Compositions for passive NOx adsorption (PNA) systems and methods of making and using same

ABSTRACT

The present disclosure relates to a substrate containing passive NO x  adsorption (PNA) materials for treatment of gases, and washcoats for use in preparing such a substrate. Also provided are methods of preparation of the PNA materials, as well as methods of preparation of the substrate containing the PNA materials. More specifically, the present disclosure relates to a coated substrate containing PNA materials for PNA systems, useful in the treatment of exhaust gases. Also disclosed are exhaust treatment systems, and vehicles, such as diesel or gasoline vehicles, particularly light-duty diesel or gasoline vehicles, using catalytic converters and exhaust treatment systems using the coated substrates.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. patentapplication Ser. No. 14/663,330, filed Mar. 19, 2015, now U.S. Pat. No.9,687,811, which claims the benefit of U.S. Provisional PatentApplication No. 61/969,035, filed Mar. 21, 2014, U.S. Provisional PatentApplication No. 61/985,388, filed Apr. 28, 2014, and U.S. ProvisionalPatent Application No. 62/121,444, filed Feb. 26, 2015. The entirecontents of those applications are hereby incorporated by referenceherein.

FIELD OF THE INVENTION

The present disclosure relates to the field of catalysts. Morespecifically, the present disclosure relates to nanoparticle catalystsand storage materials for nitrogen oxides as part of a passive NO_(x)adsorption (PNA) system for engines and vehicles.

BACKGROUND OF THE INVENTION

Car exhaust primarily contains harmful gases such as carbon monoxide(CO), nitrogen oxides (NO_(x)), and hydrocarbons (HC). Environmentalconcerns and government regulations have led efforts to remove thesenoxious combustion products from vehicle exhaust by conversion to morebenign gases such as carbon dioxide (CO₂), nitrogen (N₂), and water(H₂O). In order to accomplish this conversion, the exhaust gases mustpass through a treatment system that contains materials that can oxidizeCO to CO₂, reduce NO_(x) to N₂ and H₂O, and oxidize hydrocarbons to CO₂and H₂O.

Emission regulations and standards are becoming more and more stringentworldwide, especially for NO_(x) emissions. Two competing exhausttechnologies to reduce the amount of NO_(x) released into the atmosphereare Lean NO_(x) Traps (LNT) and Selective Catalytic Reduction (SCR).LNTs absorb, store, or trap nitrogen oxides during lean-burn engineoperation (i.e., when excess oxygen is present), and release and convertthese gases when the oxygen content in the exhaust gas is reduced. Anexample of an LNT system can be found in International PatentApplication PCT/US2014/061812 (WO 2015/061482) and U.S. ProvisionalApplication 61/894,346, which are hereby incorporated by reference intheir entirety. On the other hand, SCR units reduce nitrogen oxidesregardless of the amount of oxygen in the exhaust gas. However, SCRunits cannot properly reduce NO_(x) emissions at low operatingtemperatures, for example, temperatures below 200° C.

Unfortunately, a significant portion of pollutant gases emitted byinternal combustion engines are produced when the engine is initiallystarted (“cold-start”), but before the catalytic converters, LNTs, orSCR units in the emissions system have warmed up to their operatingtemperatures. In order to reduce harmful emissions during the cold-startphase, such as that of a light-duty diesel or gasoline vehicle (forexample, an automobile or light truck), washcoats that contain temporarystorage for pollutants can be used to coat the substrate used in thecatalytic converter of the vehicle. After the catalytic converter heatsup to its operating temperature, known as the light-off temperature (thetemperature at which the conversion rate reaches 50% of the maximumrate), the stored gases are released and subsequently decomposed by thecatalytic converter.

A high light-off temperature is undesirable, as many vehicular trips areof short duration, and during the time required for the catalyticconverter to reach its operating temperature, pollutants must either bereleased untreated to the environment, or stored in the exhaust systemuntil the light-off temperature is reached. Even if pollutants aretrapped effectively prior to light-off, the catalytic converter may notreach operating temperature if multiple successive short trips are made.Thus, the washcoats used for storage may become saturated, resultingonce again in the release of pollutants to the environment.

In addition, the exhaust temperature of an engine or vehicle can varydepending on the type of engine or vehicle. Thus, the operatingtemperature of the catalytically active material or the operatingtemperature of the SCR unit can vary depending on the engine andvehicle. For example, large engines (e.g., greater than 2.5 Liters)typically run colder than small engines (e.g., less than 2 Liters).Accordingly a tunable material used for storage of pollutants, where therelease temperature can be adjusted or tuned up or down to accommodatevarying operating temperatures in engines or vehicles, is desirable.

Commercially available catalytic converters use platinum group metal(PGM) catalysts deposited on substrates by wet chemistry methods, suchas precipitation of platinum ions, palladium ions, or platinum andpalladium ions from solution onto a substrate. These PGM catalysts are aconsiderable portion of the cost of catalytic converters. Thus, anyreduction in the amount of PGM catalysts used to produce a catalyticconverter is desirable. Commercially available catalytic converters alsodisplay a phenomenon known as “aging,” in which they become lesseffective over time; the light-off temperature starts to rise as thecatalytic converter ages, and emission levels also start to rise.Accordingly, reduction of the aging effect is also desirable, in orderto prolong the efficacy of the catalytic converter for controllingemissions.

SUMMARY OF THE INVENTION

Described herein are coated substrates for use as Passive NO_(x)Adsorbers (PNAs), washcoat formulations for preparing coated substratesfor use as PNAs, methods for preparing coated substrates for use asPNAs, and systems incorporating coated substrates employed as PNAs in anemission-control system. The disclosed PNAs can adsorb NO_(x) emissionsat low start-up temperatures, and can release the adsorbed NO_(x) atefficient operating temperatures (for example, at or above light-offtemperature) and under lean conditions.

In addition, the disclosed PNAs can reduce the amount of platinum groupmetals used in catalytic converters. At lower temperatures (temperatureswhere the T₅₀ of NO_(x) has not yet been reached), NO_(x) emissions canblock the oxidation of carbon monoxide and hydrocarbons. Thus, storingNO_(x) emissions at lower temperatures and releasing them at highertemperatures (such as temperatures above the T₅₀ temperature of NO_(x)),can decrease the amount of PGMs needed to oxidize car exhaustpollutants.

Furthermore, the PNA materials disclosed may also be able to store asmany NO_(x) emissions as possible at temperatures from ambient up to amaximum variable temperature. The maximum variable temperature canchange depending on the type of engine and vehicle employed. Thus, thedisclosed PNA materials can be tunable to store NO_(x) emissions in someinstance only up to about 100° C., in some cases up to about 150° C.,and in some cases up to about 200° C. or higher. Regardless of themaximum variable temperature, the PNA materials can exhibit a “sharp”release temperature slightly above the maximum variable temperature.

In some embodiments, the Passive NO_(x) Adsorber (PNA) composition(i.e., material) comprises nano-sized platinum group metal (PGM) on aplurality of support particles comprising cerium oxide. The plurality ofsupport particles can be micron-sized and/or nano-sized. The pluralityof support particles can include zirconium oxide, lanthanum oxide,yttrium oxide, or a combination thereof. Also, the support particles canbe HSA5, HSA20, or a mixture thereof. The nano-sized PGM on theplurality of support particles can be produced by wet chemistrytechniques and/or incipient wetness, followed by calcination. Thenano-sized PGM on the plurality of support particles can comprisecomposite nano-particles that comprise a support nanoparticle and a PGMnanoparticle. These composite nanoparticles can be bonded tomicron-sized carrier particles to form nano-on-nano-on micro particlesand/or the composite nanoparticles can be embedded within carrierparticles to form nano-on-nano-in-micro particles. The carrier particlescan comprise cerium oxide, zirconium oxide, lanthanum oxide, yttriumoxide, or a combination thereof. The carrier particles can comprise 86wt. % cerium oxide, 10 wt. % zirconium oxide, and 4 wt. % lanthanumoxide. Furthermore, the composite nano-particles can be plasma created.The PGM in the PNA composition can include palladium and/or ruthenium.The PNA composition can include 2 g/L to 4 g/L palladium including 3 g/Lpalladium. The PNA composition can include 3 g/L to 15 g/L ruthenium and5 g/L to 6 g/L ruthenium. The PNA composition can include greater thanor equal to about 150 g/L of the plurality of support particles orgreater than or equal to about 300 g/L of the plurality of supportparticles.

In some embodiments, a coated substrate comprises a substrate and aPassive NO_(x) Adsorber (“PNA”) layer comprising a PNA composition. Thevariations described above for the previously described PNA compositionare also applicable to the PNA composition recited in this coatedsubstrate. The PNA layer can store NO_(x) gas up to at least a firsttemperature and release the stored NO_(x) gas at or above the firsttemperature. The first temperature can be 150° C. or 300° C. The coatedsubstrate can be used in a greater than or equal to 2.5 L engine systemor a less than or equal to 2.5 L engine system. The PNA layer canfurther include boehmite particles. The PNA composition (including thenano-sized PGM on the plurality of support particles) can comprise 95%to 98% by weight of the mixture of the PNA composition and boehmiteparticles in the PNA layer. The boehmite particles can include 2% to 5%by weight of the mixture of the PNA composition and the boehmiteparticles in the PNA layer. The substrate can comprise cordierite and/ora honeycomb structure. The coated substrate can also include acorner-fill layer deposited directly on the substrate. The PNA layer caninclude 2 g/L to 4 g/L palladium including 3 g/L palladium. The PNAlayer can include 3 g/L to 15 g/L ruthenium and 5 g/L to 6 g/Lruthenium. The PNA layer can include greater than or equal to about 150g/L of the plurality of support particles or greater than or equal toabout 300 g/L of the plurality of support particles.

In some embodiments, a washcoat composition comprises a solids contentof 95% to 98% by weight PNA composition and 2% to 5% by weight boehmiteparticles. The variations described above for the previously describedPNA composition are also applicable to the PNA composition recited inthis washcoat composition. The solids of the wash coat composition canbe suspended in an aqueous medium at a pH between 3 and 5. The washcoatcomposition can include 2 g/L to 4 g/L palladium including 3 g/Lpalladium. The washcoat composition can include 3 g/L to 15 g/Lruthenium and 5 g/L to 6 g/L ruthenium. The washcoat composition caninclude greater than or equal to about 150 g/L of the plurality ofsupport particles or greater than or equal to about 300 g/L of theplurality of support particles.

In some embodiments, a method of treating an exhaust gas comprisescontacting a coated substrate with an exhaust gas comprising NOxemissions, wherein the coated substrate comprises a substrate and a PNAlayer. The variations described above for the previously describedcoated substrates, PNA compositions, and PNA layer are also applicableto the method of treating an exhaust gas.

In some embodiments, a method of forming a coated substrate comprisescoating the substrate with a washcoat composition comprising a PNAcomposition. The variations described above for the previously describedcoated substrates, PNA compositions, PNA layer, and washcoatcompositions are also applicable to the method of forming a coatedsubstrate. The method of forming a coated substrate can include coatingthe substrate with a corner-fill washcoat prior to coating the substratewith the PNA washcoat.

In some embodiments, a catalytic converter comprises a coated substratecomprising a PNA layer comprising a PNA composition. The variationsdescribed above for the previously described coated substrates, PNAcompositions, and PNA layers are also applicable to the method offorming a coated substrate.

In some embodiments, a vehicle comprises a catalytic convertercomprising a PNA layer comprising a PNA composition, wherein the vehiclecomplies with the European emission standard Euro 5. The variationsdescribed above for the previously described catalytic converter, PNAcompositions, and PNA layers are also applicable to the vehicle. Thevehicle can include an SCR unit downstream the catalytic converter.Also, the vehicle can include an LNT.

In some embodiments, an exhaust treatment system comprises a conduit forexhaust gas comprising NO_(x) emissions and a catalytic convertercomprising a coated substrate comprising a PNA layer comprising a PNAcomposition. The variations described above for the previously describedcoated substrates, PNA compositions, and PNA layers are also applicableto the method of forming a coated substrate. The exhaust treatmentsystem can include an SCR unit downstream the catalytic converter. Also,the vehicle can include an LNT. Furthermore, the exhaust treatmentsystem can comply with European emission standard Euro 5 and Euro 6.

In the disclosed embodiments, when a layer (layer Y) is said to beformed “on top of” another layer (layer X), either no additional layers,or any number of additional layers (layer(s) A, B, C, etc.) can beformed between the two layers X and Y. For example, if layer Y is saidto be formed on top of layer X, this can refer to a situation wherelayer X can be formed, then layer A can be formed immediately atop layerX, then layer B can be formed immediately atop layer A, then layer Y canbe formed immediately atop layer B. Alternatively, if layer Y is said tobe formed on top of layer X, this can refer to a situation where layer Ycan be deposited directly on top of layer X with no intervening layersbetween X and Y. For the specific situation where no intervening layersare present between layer X and layer Y, layer Y is said to be formedimmediately atop layer X, or equivalently, layer Y is said to be formeddirectly on top of layer X.

In some embodiments, a method of treating an exhaust gas comprisescontacting the coated substrate according to any one of the disclosed orforegoing embodiments of the coated substrate with the exhaust gas. Insome embodiments, a method of treating an exhaust gas comprisescontacting the coated substrate according to any one of the disclosed orforegoing embodiments of the coated substrate with the exhaust gas,wherein the substrate is housed within a catalytic converter configuredto receive the exhaust gas.

In some embodiments, a coated substrate comprises a washcoat accordingto any of the disclosed embodiments of the washcoat compositions.

In some embodiments, a catalytic converter comprises a coated substrateaccording to any one of the disclosed or foregoing embodiments of thecoated substrate. In some embodiments, an exhaust treatment systemcomprises a conduit for exhaust gas and a catalytic converter accordingto any one of the disclosed or foregoing embodiments of the catalyticconverter. In some embodiments, a vehicle comprises a catalyticconverter according to any one of the disclosed or foregoing embodimentsof the catalytic converter. In any of the disclosed embodiments,including the foregoing, the vehicle can comply with European emissionstandard Euro 5. In any of the disclosed embodiments, including theforegoing, the vehicle can comply with European emission standard Euro6. In any of the disclosed or foregoing embodiments the vehicle can be adiesel vehicle, a gasoline vehicle, a light-duty diesel vehicle, or alight-duty gasoline vehicle.

It is understood that aspects and embodiments of the invention describedherein include “consisting” and/or “consisting essentially of” aspectsand embodiments. For all methods, systems, compositions, and devicesdescribed herein, the methods, systems, compositions, and devices caneither comprise the listed components or steps, or can “consist of” or“consist essentially of” the listed components or steps. When a system,composition, or device is described as “consisting essentially of” thelisted components, the system, composition, or device contains thecomponents listed, and may contain other components which do notsubstantially affect the performance of the system, composition, ordevice, but either do not contain any other components whichsubstantially affect the performance of the system, composition, ordevice other than those components expressly listed; or do not contain asufficient concentration or amount of the extra components tosubstantially affect the performance of the system, composition, ordevice. When a method is described as “consisting essentially of” thelisted steps, the method contains the steps listed, and may containother steps that do not substantially affect the outcome of the method,but the method does not contain any other steps which substantiallyaffect the outcome of the method other than those steps expresslylisted.

The systems, compositions, substrates, and methods described herein,including any embodiment of the invention as described herein, may beused alone or may be used in combination with other systems,compositions, substrates, and methods.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates a catalytic converter in accordance with someembodiments of the present disclosure.

FIG. 1A is a magnified view of a portion of the drawing of FIG. 1 inaccordance with some embodiments of the present disclosure.

FIG. 2 is a flow chart illustrating a preparation method of a coatedsubstrate containing catalytically active particles, zeolites, and PNAmaterial contained in separate washcoat layers, in accordance with someembodiments of the present disclosure.

FIG. 3 is a flow chart illustrating a preparation method of a coatedsubstrate containing catalytically active particles contained in awashcoat layers, and the zeolites and PNA material contained in a singlewashcoat layer, in accordance with some embodiments of the presentdisclosure.

FIG. 4 shows a single rectangular channel in a coated substrate preparedaccording to one embodiment of the present disclosure.

FIG. 5 is a graph demonstrating the NO_(x) emission adsorption andrelease for manganese based PNA material across an operating temperaturespectrum.

FIG. 6 is a graph demonstrating the NO_(x) emission adsorption andrelease for magnesium based PNA material across an operating temperaturespectrum.

FIG. 7 is a graph demonstrating the NO_(x) emission adsorption andrelease for calcium based PNA material across an operating temperaturespectrum.

FIG. 8 is a graph demonstrating NO_(x) emission storage comparisonperformance of a catalytic converter employing PNA material as describedherein to a commercially available catalytic converter.

FIG. 9 is a graph demonstrating tailpipe emission comparison performanceof a catalytic converter employing PNA material as described herein to acommercially available catalytic converter.

DETAILED DESCRIPTION OF THE INVENTION

Described are PNA systems and methods of making PNA systems which caninclude combining washcoat layers of catalytically active particles,zeolites, and PNA materials. Also described are composite nanoparticlecatalysts, washcoat formulations, coated substrates, catalyticconverters, and methods of making and using these composite nanoparticlecatalysts, washcoat formulations, coated substrates, and catalyticconverters. The described PNA systems may use a reduced amount ofprecious metal relative to typical catalytic converter systems includinglight duty diesel systems. Accordingly, these PNA systems may provide amore economical alternative to commercially available systems.

Furthermore, the PNA materials may be able to store as many NO_(x)emissions as possible at temperatures from ambient to about 100° C.,150° C., 200° C., 250° C., or 300° C., for example. The PNA materialsmay exhibit a “sharp” release temperature under lean conditions (i.e.,releases all of the stored NO_(x) emissions at slightly above about 100°C., 150° C., 200° C., 250° C., or 300° C., for example). High releasetemperatures and/or long release “tails” are not desirable because thesehigh temperatures may not be reached prior to the engine being turnedoff. Thus, all the initially adsorbed NO_(x) emissions may not bereleased from the PNA materials before the engine is running again,therefore prohibiting adsorption repeatability in the PNA materials. Inaddition, the PNA material may be cost efficient, may be able to handlesulfur rich fuels (i.e., can be sulfurized and de-sulfurized), and canbe introduced independently to the oxidation material.

The PNA materials may also be able to store as many NO_(x) emissions aspossible at temperatures from ambient up to a maximum variabletemperature. The maximum variable temperature can change depending onthe type of engine and vehicle employed. Thus, the disclosed PNAmaterials can be tunable to store NO_(x) emissions in some instance onlyup to about 100° C., in some cases up to about 150° C., in some cases upto about 200° C., and in some cases up to about 300° C. Regardless ofthe maximum variable temperature, the PNA materials may exhibit a“sharp” release temperature slightly above the maximum variabletemperature.

In addition, the described substrates, composite nanoparticle catalysts,and washcoat solutions may provide for comparable or increasedperformance relative to prior PNA systems when used to produce catalyticconverters, allowing for the production of catalytic converters havingreduced light-off temperatures and reduced emissions using reducedplatinum group metal loading requirements. The described coatedsubstrates include washcoat layers in which the PNA material can becomposed entirely of non-PGMs, or a combination of PGM and non-PGM.These coated substrates can be used to make an effective catalyticconverter in a more economical fashion than has been previouslypossible.

The composite nanoparticles described herein include catalyticnanoparticles and support nanoparticles that are bonded together to formnano-on-nano composite nanoparticles. The composite nanoparticles may beproduced, for example, in a plasma reactor so that consistent andtightly bonded nano-on-nano composite particles are produced. Thesecomposite nanoparticles can then be bonded to a micron-sized carrierparticle to form micron-sized catalytically active particles(“nano-on-nano-on-micro” particles or NNm particles). The nano-on-nanocomposite particles are predominantly located at or near the surface ofthe resulting micron-sized particles. Alternatively, the compositenanoparticles can be embedded within a porous carrier to producemicron-sized catalytic particles (“nano-on-nano-in-micro” particles orNNiM particles). In this configuration, the nano-on-nano compositenanoparticles are distributed throughout the micron-sized carrierparticles. In addition, hybrid NNm/wet-chemistry particles can beformed. These micron-sized catalytically active particles bearingcomposite nanoparticles (i.e., NNm, NNiM, and hybrid NNm/wet-chemistryparticles) may offer better initial engine start-up performance, betterperformance over the lifetime of the catalyst and/or NO_(x) storagematerial, and/or less decrease in performance over the life of thecatalyst and/or NO_(x) storage material, as compared to previouscatalysts and NO_(x) storage materials used in catalytic converters.

Further, the washcoat formulations may be formulated in order to provideone or more layers on a catalyst substrate, such as a catalyticconverter substrate. In some embodiments, the washcoat formulations mayform two or more layers in which catalytically active material, such asmicron-sized catalytically active particles bearing composite nanoparticles, are in a separate layer than a layer containing the PNAmaterial. One embodiment, for example, is a multi-layer washcoat inwhich a first washcoat layer includes the PNA material and a second,distinct washcoat layer includes a catalytically active material (i.e.,oxidative and/or reductive material). The layer with the PNA materialmay include no catalytically active material, and the second layer withthe catalytically active material may include no PNA material. The orderand placement of these two layers on a substrate may be changed indifferent embodiments and, in further embodiments, additional washcoatformulations/layers may also be used over, under, or between thewashcoats, for example, a corner-fill washcoat layer which is initiallydeposited on the substrate to be coated or a washcoat layer containingzeolites which is deposited on the PNA washcoat layer. In otherembodiments, the two layers can be directly disposed on each other, thatis, there are no intervening layers between the first and secondwashcoat layers. The described washcoat formulations may include a loweramount of platinum group metals. In addition, the described washcoat mayoffer better performance when compared to previous washcoatformulations, particularly when these washcoat formulations utilize themicron-sized particles bearing composite nano-particles.

The coated substrates, catalytic converters, and exhaust treatmentsystems described herein are useful for vehicles employing a selectivecatalytic reduction (SCR) system, a lean NO_(x) trap (LNT) system, orother NO_(x) storage catalyst (NSC) system. It is understood that thecoated substrates described herein, catalytic converters using thecoated substrates described herein, and exhaust treatment systems usingthe coated substrates described herein useful for either gasoline ordiesel engines, and either gasoline or diesel vehicles. These coatedsubstrates, catalytic converters, and exhaust treatment systems areespecially useful for light-duty engines and light-duty vehicles,including but not limited to light-duty diesel vehicles.

Various aspects of the disclosure can be described through the use offlowcharts. Often, a single instance of an aspect of the presentdisclosure is shown. As is appreciated by those of ordinary skill in theart, however, the protocols, processes, and procedures described hereincan be repeated continuously or as often as necessary to satisfy theneeds described herein. In addition, it is contemplated that certainmethod steps can be performed in alternative sequences to thosedisclosed in the flowcharts.

When numerical values are expressed herein using the term “about” or theterm “approximately” or the symbol “˜,” it is understood that both thevalue specified, as well as values reasonably close to the valuespecified, are included. For example, the description “50° C.” or“approximately 50° C.” or “˜50° C.” includes both the disclosure of 50°C. itself, as well as values close to 50° C. Thus, the phrases “about X”or “approximately X” or “˜X” include a description of the value Xitself. If a range is indicated, such as “approximately 50° C. to 60°C.,” it is understood that both the values specified by the endpointsare included, and that values close to each endpoint or both endpointsare included for each endpoint or both endpoints; that is,“approximately 50° C. to 60° C.” is equivalent to reciting both “50° C.to 60° C.” and “approximately 50° C. to approximately 60° C.”

As used herein, the term “embedded” when describing nanoparticlesembedded in a porous carrier includes the term “bridged together by”when describing nanoparticles bridged together by a porous carrier, andrefers to the configuration of the nanoparticles in the porous carrierresulting when the porous carrier is formed around or surrounds thenanoparticles, generally by using the methods described herein. That is,the resulting structure contains nanoparticles with a scaffolding ofporous carrier between the nanoparticles, for example built up around orsurrounding the nanoparticles. The porous carrier encompasses thenanoparticles, while at the same time, by virtue of its porosity, theporous carrier permits external gases to contact the embeddednanoparticles. Nanoparticles “embedded” within a porous carrier mayinclude a configuration wherein nanoparticles are connected together(i.e., bridged together) by a carrier material.

It is generally understood by one of skill in the art that the unit ofmeasure “g/l” or “grams per liter” is used as a measure of density of asubstance in terms of the mass of the substance in any given volumecontaining that substance. In some embodiments, the “g/l” is used torefer to the loading density of a substance into, for example, a coatedsubstrate. In some embodiments, the “g/l” is used to refer to theloading density of a substance into, for example, a layer of a coatedsubstrate. In some embodiments, the “g/l” is used to refer to theloading density of a substance into, for example, a washcoatcomposition. The loading density of a substance into a layer of a coatedsubstrate can be different then the loading density of a substance intothe coated substrate. For example, if a PNA layer on the substrate isloaded with 4 g/l PGM but the layer only covers half of the substrate,then the loading density of PGM on the substrate would be 2 g/l.

By “substantial absence of any platinum group metals” is meant that lessthan about 5%, less than about 2%, less than about 1%, less than about0.5%, less than about 0.1%, less than about 0.05%, less than about0.025%, or less than about 0.01% of platinum group metals are present byweight. Preferably, substantial absence of any platinum group metalsindicates that less than about 1% of platinum group metals are presentby weight.

By “substantially free of” a specific component, a specific composition,a specific compound, or a specific ingredient in various embodiments, ismeant that less than about 5%, less than about 2%, less than about 1%,less than about 0.5%, less than about 0.1%, less than about 0.05%, lessthan about 0.025%, or less than about 0.01% of the specific component,the specific composition, the specific compound, or the specificingredient is present by weight. Preferably, “substantially free of” aspecific component, a specific composition, a specific compound, or aspecific ingredient indicates that less than about 1% of the specificcomponent, the specific composition, the specific compound, or thespecific ingredient is present by weight.

It should be noted that, during fabrication or during operation(particularly over long periods of time), small amounts of materialspresent in one washcoat layer may diffuse, migrate, or otherwise moveinto other washcoat layers. Accordingly, use of the terms “substantialabsence of” and “substantially free of” is not to be construed asabsolutely excluding minor amounts of the materials referenced.

By “substantially each” of a specific component, a specific composition,a specific compound, or a specific ingredient in various embodiments, ismeant that at least about 95%, at least about 98%, at least about 99%,at least about 99.5%, at least about 99.9%, at least about 99.95%, atleast about 99.975%, or at least about 99.99% of the specific component,the specific composition, the specific compound, or the specificingredient is present by number or by weight. Preferably, “substantiallyeach” of a specific component, a specific composition, a specificcompound, or a specific ingredient is meant that at least about 99% ofthe specific component, the specific composition, the specific compound,or the specific ingredient is present by number or by weight.

This disclosure provides several embodiments. It is contemplated thatany features from any embodiment can be combined with any features fromany other embodiment. In this fashion, hybrid configurations of thedisclosed features are within the scope of the present invention.

It is understood that reference to relative weight percentages in acomposition assumes that the combined total weight percentages of allcomponents in the composition add up to 100. It is further understoodthat relative weight percentages of one or more components may beadjusted upwards or downwards such that the weight percent of thecomponents in the composition combine to a total of 100, provided thatthe weight percent of any particular component does not fall outside thelimits of the range specified for that component.

This disclosure refers to both particles and powders. These two termsare equivalent, except for the caveat that a singular “powder” refers toa collection of particles. The present disclosure can apply to a widevariety of powders and particles. The terms “nanoparticle” and“nano-sized particle” are generally understood by those of ordinaryskill in the art to encompass a particle on the order of nanometers indiameter, typically between about 0.5 nm to 500 nm, about 1 nm to 500nm, about 1 nm to 100 nm, or about 1 nm to 50 nm. The nanoparticles canhave an average grain size less than 250 nanometers and an aspect ratiobetween one and one million. In some embodiments, the nanoparticles havean average grain size of about 50 nm or less, about 30 nm or less, about20 nm or less, about 10 nm or less, or about 5 nm or less. In additionalembodiments, the nanoparticles have an average diameter of about 50 nmor less, about 30 nm or less, about 20 nm or less, about 10 nm or less,or about 5 nm or less. The aspect ratio of the particles, defined as thelongest dimension of the particle divided by the shortest dimension ofthe particle, is preferably between one and one hundred, more preferablybetween one and ten, yet more preferably between one and two. “Grainsize” is measured using the ASTM (American Society for Testing andMaterials) standard (see ASTM E112-10). When calculating a diameter of aparticle, the average of its longest and shortest dimension is taken;thus, the diameter of an ovoid particle with long axis 20 nm and shortaxis 10 nm would be 15 nm. The average diameter of a population ofparticles is the average of diameters of the individual particles, andcan be measured by various techniques known to those of skill in theart.

In additional embodiments, the nanoparticles have a grain size of about50 nm or less, about 30 nm or less, about 20 nm or less, about 10 nm orless, or about 5 nm or less. In additional embodiments, thenanoparticles have a diameter of about 50 nm or less, about 30 nm orless, about 20 nm or less, about 10 nm or less, or about 5 nm or less.

The terms “micro-particle,” “micro-sized particle,” “micron-particle,”and “micron-sized particle” are generally understood to encompass aparticle on the order of micrometers in diameter, typically betweenabout 0.5 μm to 1000 μm, about 1 μm to 1000 μm, about 1 μm to 100 μm, orabout 1 μm to 50 μm. Additionally, the term “platinum group metals”(abbreviated “PGM”) used in this disclosure refers to the collectivename used for six metallic elements clustered together in the periodictable. The six platinum group metals are ruthenium, rhodium, palladium,osmium, iridium, and platinum.

Composite Nanoparticles

PNA systems may include many different types of composite nanoparticles.One type of composite nanoparticle is an oxidative compositenanoparticle. A second type of composite nanoparticle is a PNA compositenanoparticle. The PNA systems can also include reductive compositenanoparticles as well.

A composite nanoparticle may include a catalytic nanoparticle attachedto a support nanoparticle to form a “nano-on-nano” compositenanoparticle. Multiple nano-on-nano particles may then be bonded to orembedded within a micron-sized carrier particle to form a compositemicro/nanoparticle, that is, a micro-particle bearing compositenanoparticles. These composite micro/nanoparticles may be used inwashcoat formulations and catalytic converters as described herein. Theuse of these particles can reduce requirements for platinum group metalcontent and significantly enhance performance, particularly in terms ofreduced light-off temperature and NO_(x) storage, as compared withcurrently available commercial catalytic converters prepared bywet-chemistry methods. The wet-chemistry methods generally involve useof a solution of platinum group metal ions or metal salts, which areimpregnated into supports (typically micron-sized particles), andreduced to platinum group metal in elemental form for use as thecatalyst. For example, a solution of chloroplatinic acid, H₂PtCl₆, canbe applied to alumina micro-particles, followed by drying and calcining,resulting in precipitation of platinum onto the alumina. In anyembodiment, the drying and/or calcining can be done under reducingconditions as compared to atmospheric conditions in order to limit theamount of oxide formation (specifically, with regard to the PGM metal).Accordingly, the drying and/or calcining can be done using argon and/orhelium. The platinum group metals deposited by wet-chemical methods ontometal oxide supports, such as alumina and cerium oxide, are mobile athigh temperatures, such as temperatures encountered in catalyticconverters. That is, at elevated temperatures, the PGM atoms can migrateover the surface on which they are deposited, and will clump togetherwith other PGM atoms. The finely-divided portions of PGM combine intolarger and larger agglomerations of platinum group metal as the time ofexposure to high temperature increases. This agglomeration leads toreduced catalyst surface area and degrades the performance of thecatalytic converter. This phenomenon is referred to as “aging” of thecatalytic converter.

In contrast, the composite platinum group metal particles are preparedby plasma-based methods. In one embodiment, the platinum groupnano-sized metal particle is deposited on a nano-sized metal oxidesupport, which has much lower mobility than PGM deposited by wetchemistry methods. The resulting plasma-produced catalysts age at a muchslower rate than the catalysts produced by wet-chemistry. Thus,catalytic converters using plasma-produced catalysts can maintain alarger surface area of exposed catalyst to gases emitted by the engineover a longer period of time, leading to better emissions performance.

Oxidative Composite Nanoparticle (Oxidative “Nano-on-Nano” Particle)

One type of composite nanoparticle is an oxidative compositenanoparticle catalyst. An oxidative composite nanoparticle may includeone or more oxidative catalyst nanoparticles attached to a first supportnanoparticle to form an oxidative “nano-on-nano” composite nanoparticle.Platinum (Pt) and palladium (Pd) are oxidative to the hydrocarbon gasesand carbon monoxide. In certain embodiments, the oxidative nanoparticleis platinum. In other embodiments, the oxidative nanoparticle ispalladium. In some embodiments, the oxidative nanoparticle is a mixtureof platinum and palladium. A suitable support nanoparticle for theoxidative catalyst nanoparticle includes, but is not limited to,nano-sized aluminum oxide (alumina or Al₂O₃).

Each oxidative catalyst nanoparticle may be supported on a first supportnanoparticle. The first support nanoparticle may include one or moreoxidative nanoparticles. The oxidative catalyst nanoparticles on thefirst support nanoparticle may include platinum, palladium, or a mixturethereof. At the high temperatures involved in gasoline or diesel exhaustengines, both palladium and platinum are effective oxidative catalysts.Accordingly, in some embodiments, the oxidative catalyst is palladiumalone. In other embodiments, platinum may be used alone. In furtherembodiments, platinum may be used in combination with palladium. Forexample, the first support nanoparticle may contain a mixture of 2:1 to100:1 platinum to palladium. In some embodiments, the first supportnanoparticle may contain a mixture of 2:1 to 75:1 platinum to palladium.In some embodiments, the first support nanoparticle may contain amixture of 2:1 to 50:1 platinum to palladium. In some embodiments, thefirst support nanoparticle may contain a mixture of 2:1 to 25:1 platinumto palladium. In some embodiments, the first support nanoparticle maycontain a mixture of 2:1 to 15:1 platinum to palladium. In someembodiments, the first support nanoparticle may contain a mixture of 2:1to 10:1 platinum to palladium. In some embodiments, the first supportnanoparticle may contain a mixture of 2:1 to 5:1 platinum to palladium.In some embodiments, the first support nanoparticle may contain amixture of 2:1 platinum to palladium, or approximately 2:1 platinum topalladium. In some embodiments, the support particles may contain amixture of 2:1 to 20:1 platinum to palladium. In some embodiments, thesupport particles may contain a mixture of 5:1 to 15:1 platinum topalladium. In some embodiments, the support particles may contain amixture of 8:1 to 12:1 platinum to palladium. In some embodiments, thesupport particles may contain a mixture of 10:1 platinum to palladium,or approximately 10:1 platinum to palladium. In some embodiments, thesupport particles may contain a mixture of 2:1 to 8:1 platinum topalladium. In some embodiments, the support particles may contain amixture of 3:1 to 5:1 platinum to palladium. In some embodiments, thesupport particles may contain a mixture of 4:1 platinum to palladium, orapproximately 4:1 platinum to palladium.

Reductive Composite Nanoparticle (Reductive “Nano-on-Nano” Particle)

As discussed above, another type of composite nanoparticle is areductive composite nanoparticle catalyst. A reductive compositenanoparticle may include one or more reductive catalyst nanoparticlesattached to a second support nanoparticle to form a reductive“nano-on-nano” composite nanoparticle. Rhodium (Rh) is reductive to thenitrogen oxides in fuel-rich conditions. In certain embodiments, thereductive catalyst nanoparticle is rhodium. The second support may bethe same or different than the first support. A suitable second supportnanoparticle for the reductive nanoparticle includes, but is not limitedto, nano-sized cerium oxide (CeO₂). The nano-sized cerium oxideparticles may further comprise zirconium oxide. The nano-sized ceriumoxide particles can also be substantially free of zirconium oxide. Inother embodiments, the nano-sized cerium oxide particles may contain upto 60% zirconium oxide. In some embodiments, the nano-sized cerium oxideparticles may further comprise both zirconium oxide and lanthanum and/orlanthanum oxide. In some embodiments, the nano-sized cerium oxideparticles may further comprise yttrium oxide. Accordingly, in additionto, or instead of, cerium oxide particles, particles comprisingcerium-zirconium oxide, cerium-lanthanum oxide, cerium-yttrium oxide,cerium-zirconium oxide, cerium-zirconium-yttrium oxide,cerium-lanthanum-yttrium oxide, and/orcerium-zirconium-lanthanum-yttrium oxide can be used. In someembodiments, the nano-sized cerium oxide particles contain 40-90 wt %cerium oxide, 5-60 wt % zirconium oxide, 1-15 wt % lanthanum oxide,and/or 1-10 wt % yttrium oxide. In one embodiment, the nano-sized ceriumoxide particles contain 80 wt % cerium oxide, 10 wt % zirconium oxide,and 10 wt % lanthanum and/or lanthanum oxide. In another embodiment, thenano-sized cerium oxide particles contain 86 wt % cerium oxide, 10 wt %zirconium oxide, and 4 wt % lanthanum oxide. In another embodiment, thenano-sized cerium oxide particles contain 40 wt % cerium oxide, 50 wt %zirconium oxide, and 10 wt % lanthanum and/or lanthanum oxide. Inanother embodiment, the cerium oxide particles contain 40 wt % ceriumoxide, 50 wt % zirconium oxide, 5 wt % lanthanum oxide, and 5 wt %yttrium oxide.

Each reductive catalyst nanoparticle may be supported on a secondsupport nanoparticle. The second support nanoparticle may include one ormore reductive catalyst nanoparticles. The ratios of rhodium to ceriumoxide and sizes of the reductive composite nanoparticle catalyst arefurther discussed below in the sections describing production ofcomposite nanoparticles by plasma-based methods and production ofmicron-sized carrier particles bearing composite nanoparticles.

PNA Composite Nanoparticle (PNA “Nano-on-Nano” Particle)

As discussed above, another type of composite nanoparticle is a PNAcomposite nanoparticle. A PNA composite nanoparticle may include one ormore PGM nanoparticles attached to a second support nanoparticle to forma PGM “nano-on-nano” composite nanoparticle. Palladium (Pd) andRuthenium (Ru) can hold NO_(x) gases during low temperature engineoperation and release the gases when the temperature rises to athreshold temperature. In certain embodiments, the PGM nanoparticle ispalladium. In some embodiments, palladium can be used when employed in alarge engine system (e.g., greater than 2.5 L). In other embodiments,the PGM nanoparticle is ruthenium. In some embodiments, ruthenium can beused when employed in a small engine system (e.g., less than 2 L). Theruthenium can be ruthenium oxide. A suitable second support nanoparticlefor the PGM nanoparticle includes, but is not limited to, nano-sizedcerium oxide. The nano-sized cerium oxide particles may further comprisezirconium oxide. The nano-sized cerium oxide particles can also besubstantially free of zirconium oxide. In addition, the nano-sizedcerium oxide may further comprise lanthanum and/or lanthanum oxide. Insome embodiments, the nano-sized cerium oxide particles may furthercomprise both zirconium oxide and lanthanum oxide. In some embodiments,the nano-sized cerium oxide particles may further comprise yttriumoxide. Accordingly, in addition to, or instead of, cerium oxideparticles, particles comprising cerium-zirconium oxide, cerium-lanthanumoxide, cerium-yttrium oxide, cerium-zirconium oxide,cerium-zirconium-yttrium oxide, cerium-lanthanum-yttrium oxide, and/orcerium-zirconium-lanthanum-yttrium oxide can be used. In someembodiments, the nano-sized cerium oxide particles contain 40-90 wt %cerium oxide, 5-60 wt % zirconium oxide, 1-15 wt % lanthanum oxide,and/or 1-10 wt % yttrium oxide. In one embodiment, the nano-sized ceriumoxide particles contain 86 wt % cerium oxide, 10 wt % zirconium oxide,and 4 wt % lanthanum and/or lanthanum oxide. In another embodiment, thecerium oxide particles contain 40 wt % cerium oxide, 50 wt % zirconiumoxide, 5 wt % lanthanum oxide, and 5 wt % yttrium oxide.

Each PGM nanoparticle may be supported on a second support nanoparticle.The second support nanoparticle may include one or more PGMnanoparticles. The ratios of PGM to cerium oxide and sizes of the PNAcomposite nanoparticle catalyst are further discussed below in thesections describing production of composite nanoparticles byplasma-based methods and production of micron-sized carrier particlesbearing composite nanoparticles.

Production of Composite Nanoparticles by Plasma-Based Methods(“Nano-on-Nano” Particles or “NN” Particles)

The initial step in producing suitable catalysts may involve producingcomposite nano-particles. The composite nano-particles comprise acatalytic nano-particle comprising one or more platinum group metals,and a support nano-particle, typically a metal oxide such as aluminumoxide or cerium oxide. As the name “nano-particle” implies, thenano-particles have sizes on the order of nanometers.

The composite nano-particles may be formed by plasma reactor methods, byfeeding platinum group metal(s) and support material into a plasma gun,where the materials are vaporized. Plasma guns such as those disclosedin US 2011/0143041 can be used, and techniques such as those disclosedin U.S. Pat. No. 5,989,648, U.S. Pat. No. 6,689,192, U.S. Pat. No.6,755,886, and US 2005/0233380 can be used to generate plasma, thedisclosures of which are hereby incorporated by reference in theirentireties. A working gas, such as argon, is supplied to the plasma gunfor the generation of plasma; in one embodiment, an argon/hydrogenmixture (in the ratio of 10:2 Ar/H₂) is used as the working gas.

The platinum group metal or metals, such as platinum, palladium, orruthenium, and which are generally in the form of metal particles ofabout 0.5 to 6 microns in diameter, can be introduced into the plasmareactor as a fluidized powder in a carrier gas stream such as argon.Metal oxide, typically aluminum oxide or cerium oxide in a particle sizeof about 15 to 25 microns diameter, is also introduced as a fluidizedpowder in carrier gas. However, other methods of introducing thematerials into the reactor can be used, such as in a liquid slurry. Acomposition of about 1% to about 40% platinum group metal(s) and about99% to about 60% metal oxide (by weight) can be used. Furthermore, acomposition of about 40% to about 60% platinum group metal(s) and about60% to about 40% metal oxide (by weight) can be used. Examples of rangesof materials that can be used for oxidative composite nanoparticles arefrom about 0% to about 40% platinum, about 0% to about 40% palladium,and about 55% to about 65% aluminum oxide; in some embodiments, fromabout 20% to about 30% platinum, about 10% to about 15% palladium, andabout 50% to about 65% aluminum oxide are used; in further embodiments,from about 23.3% to about 30% platinum, about 11.7% to about 15%palladium, and about 55% to about 65% aluminum oxide are used. Anexemplary composition contains about 26.7% platinum, about 13.3%palladium, and about 60% aluminum oxide.

The oxidative composite nanoparticles may contain a mixture of 2:1 to100:1 platinum to palladium. In some embodiments, the oxidativecomposite nanoparticles may contain a mixture of 2:1 to 75:1 platinum topalladium. In some embodiments, the oxidative composite nanoparticlesmay contain a mixture of 2:1 to 50:1 platinum to palladium. In someembodiments, the oxidative composite nanoparticles may contain a mixtureof 2:1 to 25:1 platinum to palladium. In some embodiments, the oxidativecomposite nanoparticles may contain a mixture of 2:1 to 15:1 platinum topalladium. In some embodiments, the oxidative composite nanoparticlesmay contain a mixture of 2:1 to 10:1 platinum to palladium. In someembodiments, the oxidative composite nanoparticles may contain a mixtureof 2:1 platinum to palladium, or approximately 2:1 platinum topalladium. In some embodiments, the support particles may contain amixture of 2:1 to 20:1 platinum to palladium. In some embodiments, thesupport particles may contain a mixture of 5:1 to 15:1 platinum topalladium. In some embodiments, the support particles may contain amixture of 8:1 to 12:1 platinum to palladium. In some embodiments, thesupport particles may contain a mixture of 10:1 platinum to palladium,or approximately 10:1 platinum to palladium. In some embodiments, thesupport particles may contain a mixture of 2:1 to 8:1 platinum topalladium. In some embodiments, the support particles may contain amixture of 3:1 to 5:1 platinum to palladium. In some embodiments, thesupport particles may contain a mixture of 4:1 platinum to palladium, orapproximately 4:1 platinum to palladium.

Examples of ranges of materials that can be used for reductive compositenanoparticles are from about 1% to about 10% rhodium and 90% to 99%cerium oxide. In one embodiment, the composition contains about 5%rhodium and 95% cerium oxide.

Examples of ranges of materials that can be used for PNA compositenanoparticles are from about 1% to about 40% palladium and about 99% toabout 60% cerium oxide, from about 5% to about 20% palladium and about95% to about 80% cerium oxide, and from about 8% to about 12% palladiumand about 92% to about 88% cerium oxide. These examples can be for PNAmaterial to be used in large engine systems. In one embodiment, thecomposition contains about 10% palladium and about 90% cerium oxide.Other Examples of ranges of materials that can be used for PNA compositenanoparticles are from about 1% to about 40% ruthenium and about 99% toabout 60% cerium oxide, from about 5% to about 20% ruthenium and about95% to about 80% cerium oxide, and from about 8% to about 12% rutheniumand about 92% to about 88% cerium oxide. These examples can be for PNAmaterial to be used in small engine systems. In one embodiment, thecomposition contains about 10% ruthenium and about 90% cerium oxide. Asdiscussed below, in all embodiments, the cerium oxide can includecerium-zirconium oxide, cerium-zirconium-lanthanum oxide, andcerium-zirconium-lanthanum-yttrium oxide among others.

In a plasma reactor, any solid or liquid materials are rapidly vaporizedor turned into plasma. The kinetic energy of the superheated material,which can reach temperatures of 20,000 to 30,000 Kelvin, ensuresextremely thorough mixture of all components.

The superheated material of the plasma stream is then rapidly quenched,using methods such as the turbulent quench chamber disclosed in U.S.Publication No. 2008/0277267, the disclosure of which is herebyincorporated by reference in their entireties. Argon quench gas at highflow rates, such as 2400 to 2600 liters per minute, may be injected intothe superheated material. The material may be further cooled in acool-down tube, and collected and analyzed to ensure proper size rangesof material.

The plasma production method described above produces highly uniformcomposite nanoparticles, where the composite nanoparticles comprise acatalytic nanoparticle bonded to a support nanoparticle. The catalyticnanoparticle comprises the platinum group metal or metals, such as Pt:Pdin a 2:1 ratio by weight. In some embodiments, the catalyticnanoparticles have an average diameter or average grain size betweenapproximately 0.3 nm and approximately 10 nm, preferably betweenapproximately 1 nm to approximately 5 nm, that is, approximately 3 nm±2nm. These size of catalytic nanoparticles can be the size of thecatalytic nanoparticles employed when using wet chemistry methods. Insome embodiments, the support nanoparticles, comprising the metal oxidesuch as aluminum oxide or cerium oxide, have an average diameter ofapproximately 20 nm or less, or approximately 15 nm or less, or betweenapproximately 10 nm and approximately 20 nm, that is, approximately 15nm±5 nm, or between approximately 10 nm and approximately 15 nm, thatis, approximately 12.5 nm±2.5 nm, or between approximately 5 nm andapproximately 10 nm, that is, approximately 7.5 nm±2.5 nm.

The composite nanoparticles, when produced under reducing conditions,such as by using argon/hydrogen working gas, results in a partiallyreduced surface on the support nanoparticle to which the PGMnanoparticle is bonded, as described in U.S. Publication No.2011/0143915 at paragraphs 0014-0022. For example, when palladium ispresent in the plasma, the particles produced under reducing conditionscan be a palladium aluminate. The partially reduced surface inhibitsmigration of the platinum group metal on the support surface at hightemperatures. This, in turn, limits the agglomeration of platinum groupmetal when the particles are exposed to prolonged elevated temperatures.Such agglomeration is undesirable for many catalytic applications, as itreduces the surface area of PGM catalyst available for reaction.

The composite nanoparticles comprising two nanoparticles (catalytic orsupport) are referred to as “nano-on-nano” particles or “NN” particles.

Production of Micron-Sized Carrier Particles Bearing CompositeNanoparticles (“Nano-on-Nano-on-Micro” Particles or “NNm”™ Particles)

The composite nanoparticles (nano-on-nano particles) may be furtherbonded to micron-sized carrier particles to produce compositemicro/nanoparticles, referred to as “nano-on-nano-on-micro” particles or“NNm”™ particles, which are catalytically active particles.

The micron-sized particles can have an average size between about 1micron and about 100 microns, such as between about 1 micron and about10 microns, between about 3 microns and about 7 microns, or betweenabout 4 microns and about 6 microns. In one embodiment, the micron-sizedparticles have an average size of 5 microns. These sizes of micron-sizedparticles can be the size of the micron-sized particles employed whenusing wet chemistry methods.

In general, the nano-on-nano-on-micro particles are produced by aprocess of suspending the composite nanoparticles (nano-on-nanoparticles) in water, adjusting the pH of the suspension to between about2 and about 7, between about 3 and about 5, or about 4, adding one ormore surfactants to the suspension (or, alternatively, adding thesurfactants to the water before suspending the composite nanoparticlesin the water) to form a first solution. The process includes sonicatingthe composite nanoparticle suspension and applying the suspension tomicron-sized metal oxide particles until the point of incipient wetness,thereby impregnating the micron-sized particles with compositenanoparticles and nano-sized metal oxide. This process of drying andcalcining can also be applied to producing nanoparticles on supportparticles (either micron-sized or on nano-sized) via incipient wetnessin general.

In some embodiments, the micron-sized metal oxide particles arepre-treated with a gas at high temperature. The pre-treatment of themicron-sized metal oxide particles allows the nano-on-nano-on-microparticles to withstand the high temperatures of an engine. Withoutpre-treatment, the nano-on-nano-on-micro particles would more likelychange phase on exposure to high temperature, compared to thenano-on-nano-on-micro particles that have been pretreated. In someembodiments, pre-treatment includes exposure of the micron-sized metaloxide particles at temperatures, such as about 700° C. to about 1500°C.; 700° C. to about 1400° C.; 700° C. to about 1300° C.; and 700° C. toabout 1200° C. In some embodiments, pre-treatment includes exposure ofthe micron-sized metal oxide particles at temperatures, such as about700° C., 1110° C., 1120° C., 1130° C., 1140° C., 1150° C., 1155° C.,1160° C., 1165° C., 1170° C., 1175° C., 1180° C., 1190° C., and 1200° C.

The process includes drying the micron-sized metal oxide particles whichhave been impregnated with composite nanoparticles and nano-sized metaloxide, and calcining the micron-sized metal oxide particles which havebeen impregnated with composite nanoparticles and nano-sized metaloxide.

Typically, the composite nanoparticles and nano-sized metal oxide aresuspended in water, and the suspension is adjusted to have a pH ofbetween about 2 and about 7, preferably between about 3 and about 5,more preferably a pH of about 4 (the pH is adjusted with acetic acid oranother organic acid). Dispersants, surfactants, or mixtures thereof maybe added to the composite nanoparticles and nano-sized metal oxide.Surfactants suitable for use include Jeffsperse® X3202 (ChemicalAbstracts Registry No. 68123-18-2, described as4,4′-(1-methylethylidene)bis-phenol polymer with2-(chloromethyl)oxirane, 2-methyloxirane, and oxirane), Jeffsperse®X3204, and Jeffsperse® X3503 surfactants from Huntsman (JEFFSPERSE is aregistered trademark of Huntsman Corporation, The Woodlands, Tex.,United States of America for chemicals for use as dispersants andstabilizers), which are non-ionic polymeric dispersants. Other suitablesurfactants include Solsperse® 24000 and Solsperse® 46000 from Lubrizol(SOLSPERSE is a registered trademark of Lubrizol Corporation,Derbyshire, United Kingdom for chemical dispersing agents). TheJeffsperse® X3202 surfactant, Chemical Abstracts Registry No. 68123-18-2(described as 4,4′-(1-methylethylidene)bis-phenol polymer with2-(chloromethyl)oxirane, 2-methyloxirane, and oxirane), is preferred.The surfactant may be added in a range, for example, of about 0.5% toabout 5%, with about 2% being a typical value.

The mixture of aqueous surfactants, composite nanoparticles, andnano-sized metal oxide may be sonicated to disperse the compositenanoparticles and nano-sized metal oxide. The quantity of compositenanoparticles and nano-sized metal oxide in the dispersion may be in therange of about 2% to about 15% (by mass). The dispersion is then appliedto porous, micron sized metal oxides, such as Al₂O₃ which may bepurchased from companies such as Rhodia or Sasol or cerium oxide. Theporous, micron sized, metal oxide powders may be stabilized with a smallpercentage of lanthanum and/or lanthanum oxide (about 2% to about 4%La). In addition, the porous, micron sized, metal oxide powder mayinclude a percentage of zirconium oxide (about 5% to about 15%,preferably 10%). In some embodiments, the porous, micron sized, metaloxide powders may further comprise yttrium oxide. Accordingly, theporous, micron sized, metal oxide powders can include cerium oxide,cerium-zirconium oxide, cerium-lanthanum oxide, cerium-yttrium oxide,cerium-zirconium-lanthanum oxide, cerium-zirconium-yttrium oxide,cerium-lanthanum-yttrium oxide, cerium-zirconium-lanthanum-yttriumoxide, or a combination thereof. In some embodiments, the nano-sizedcerium oxide particles contain 40-90 wt % cerium oxide, 5-60 wt %zirconium oxide, 1-15 wt % lanthanum oxide, and/or 1-10 wt % yttriumoxide. In one embodiment, the micron-sized cerium oxide particlescontain 86 wt % cerium oxide, 10 wt % zirconium oxide, and 4 wt %lanthanum and/or lanthanum oxide. In another embodiment, the ceriumoxide particles contain 40 wt % cerium oxide, 50 wt % zirconium oxide, 5wt % lanthanum oxide, and 5 wt % yttrium oxide. One commercial aluminapowder suitable for use is MI-386, purchased from Grace Davison orRhodia. The usable surface for this powder, defined by pore sizesgreater than 0.28 μm, is approximately 2.8 m²/g. One commercial ceriumoxide powder suitable for use is HSA5, HSA20, or a mixture thereof,purchased from Rhodia-Solvay.

The ratio of composite nano-particles used to micron-sized carrierparticles used may be from about 3:100 to about 10:100, about 5:100 toabout 8:100, or about 6.5:100, in terms of (weight of compositenanoparticle):(weight of micron carrier particle). In some embodiments,about 8 grams of composite nano-particles may be used with about 122grams of carrier micro-particles. The aqueous dispersion of compositenano-particles is applied in small portions (such as by dripping orother methods) to the micron-sized powder until the point of incipientwetness, producing a material similar to damp sand.

The micron-sized carrier particles, impregnated with the compositenano-particles, may then be dried (for example, at about 30° C. to about95° C., preferably about 60° C. to about 70° C., at atmospheric pressureor at reduced pressure such as from about 1 pascal to about 90,000pascal). After drying, the particles may then be calcined (at elevatedtemperatures, such as from 400° C. to about 700° C., preferably about500° C. to about 600° C., more preferably at about 540° C. to about 560°C., still more preferably at about 550° C. to about 560° C., or at about550° C.; at atmospheric pressure or at reduced pressure, for example,from about 1 pascal to about 90,000 pascal, in ambient atmosphere orunder an inert atmosphere such as nitrogen or argon) to yield thecomposite micro/nano-particles, also referred to asnano-on-nano-on-micron particles, or NNm particles. The drying step maybe performed before the calcining step to remove the water beforeheating at the higher calcining temperatures; this avoids boiling of thewater, which would disrupt the impregnated nano-particles which arelodged in the pores of the micron-sized carrier. In any embodiment, thedrying and/or calcining can be done under reducing conditions ascompared to atmospheric conditions in order to limit the amount of oxideformation (specifically, with regard to the PGM metal). Accordingly, thedrying and/or calcining can be done using argon and/or helium.

The NNm particles may contain from about 0.1% to about 6% PGM by weight,or in another embodiment from about 0.5% to 3.5% by weight, or inanother embodiment about 1% to 2.5% by weight, or in another embodimentabout 2% to about 3% by weight, or in another embodiment, about 2.5% byweight, of the total mass of the NNm particle. The NNm particles canthen be used for formulations for coating substrates, where the coatedsubstrates may be used in catalytic converters.

Examples of production of NNm material are described in the followingco-owned patents and patent applications the disclosures of which arehereby incorporated by reference in their entireties: U.S. PatentPublication No. 2005/0233380, U.S. Patent Publication No. 2006/0096393,U.S. patent application Ser. No. 12/151,810 (now abandoned), U.S. patentapplication Ser. No. 12/152,084 (now abandoned), U.S. patent applicationSer. No. 12/151,809 (now abandoned), U.S. Pat. No. 7,905,942, U.S.patent application Ser. No. 12/152,111 (now abandoned), U.S. PatentPublication 2008/0280756, U.S. Patent Publication 2008/0277270, U.S.patent application Ser. No. 12/001,643 (now U.S. Pat. No. 8,507,401),U.S. patent application Ser. No. 12/474,081 now U.S. Pat. No.8,507,402), U.S. patent application Ser. No. 12/001,602 (now U.S. Pat.No. 8,575,059), U.S. patent application Ser. No. 12/001,644 now U.S.Pat. No. 8,481,449), U.S. patent application Ser. No. 12/962,518 (U.S.Patent Publication 2011/0143930), now abandoned, U.S. patent applicationSer. No. 12/962,473 (now U.S. Pat. No. 8,652,992), U.S. patentapplication Ser. No. 12/962,490 (now U.S. Pat. No. 9,126,191), U.S.patent application Ser. No. 12/969,264 (U.S. Patent Publication2011-0144382), now abandoned, U.S. patent application Ser. No.12/962,508 (now U.S. Pat. No. 8,557,727), U.S. patent application Ser.No. 12/965,745 (now U.S. Pat. No. 9,149,797), U.S. patent applicationSer. No. 12/969,503 (now U.S. Pat. No. 8,828,328), and U.S. patentapplication Ser. No. 13/033,514 (now U.S. Pat. No. 8,669,202), WO2011/081834 (PCT/US2010/59763) and US 2011/0143915 (U.S. patentapplication Ser. No. 12/962,473, now U.S. Pat. No. 8,652,992).

Production of Hybrid Micron-Sized Carrier Particles Bearing CompositeNanoparticles (“Nano-on-Nano-on-Micro” Particles or “NNm”™ Particles)and Also Impregnated with Platinum Group Metal(s) Using Wet ChemistryMethods—“Hybrid NNm/Wet-Chemistry Particles” or “HybridComposite/Wet-Chemistry Particles”

Furthermore, the micron-sized particles which bear the compositenanoparticles can additionally be impregnated with platinum group metalsusing wet-chemistry methods, so that PGM is present on the micron-sizedparticle due to the nano-on-nano composite nanoparticles and also due tothe deposition via wet chemistry. The micron-sized particles can beimpregnated with PGM before or after the composite nanoparticles(nano-on-nano) are bonded to the micron-sized particles. When thenano-on-nano particles are added to the micron-sized carrier particles,the nano-on-nano particles tend to stay near the surface of the micronparticle, as they are too large to penetrate into the smaller pores ofthe micron particle. Therefore, impregnating these micron-sizedparticles via wet-chemistry methods allows for PGM to penetrate deeperinto the micron-sized particles than the corresponding nano-on-nanoparticles. In addition, because the nano-on-nano particles of thesehybrid NNm/wet-chemistry particles contain PGM, lower amounts of PGM canbe impregnated by wet-chemistry on the micron-sized particles to achievethe total desired loading. For example, if a final loading of 5 g/l ofPGM is desired on the final catalyst or PNA material, loading 3 g/l ofPGM as nano-on-nano (NN) particles requires only 2 g/l of PGM to beloaded via wet-chemistry methods. A lower amount of wet-chemistryimpregnated PGM can reduce the agglomeration rate of these wet-chemistryimpregnated catalytic particles when the catalyst or PNA material isexposed to prolonged elevated temperatures since there is less PGM toagglomerate. That is, the rate of aging of the catalyst will be reduced,since the rate of collision and agglomeration of mobilewet-chemistry-deposited PGM is reduced at a lower concentration of thewet-chemistry-deposited PGM, but without lowering the overall loading ofPGM due to the contribution of PGM from the nano-on-nano particles.Thus, employing the nano-on-nano-on-micro configuration and using amicron-sized particle with wet-chemistry deposited platinum group metalcan enhance catalyst performance and NO_(x) storage while avoiding anexcessive aging rate.

Methods for impregnation of carriers and production of catalysts by wetchemistry methods are discussed in Heck, Ronald M.; Robert J. Farrauto;and Suresh T. Gulati, Catalytic Air Pollution Control: CommercialTechnology, Third Edition, Hoboken, N.J.: John Wiley & Sons, 2009, atChapter 2, pages 24-40 (see especially pages 30-32) and referencesdisclosed therein, and also in Marceau, Eric; Xavier Carrier, and MichelChe, “Impregnation and Drying,” Chapter 4 of Synthesis of SolidCatalysts (Editor: de Jong, Krijn) Weinheim, Germany: Wiley-VCH, 2009,at pages 59-82 and references disclosed therein.

For wet chemistry impregnation, typically a solution of a platinum groupmetal salt is added to the micron sized carrier particle to the point ofincipient wetness, followed by drying, calcination, and reduction asnecessary to elemental metal. Platinum can be deposited on carriers suchas alumina by using Pt salts such as chloroplatinic acid H₂PtCl₆),followed by drying, calcining, and reduction to elemental metal.Palladium can be deposited on carriers such as alumina using salts suchas palladium nitrate (Pd(NO₃)₂), palladium chloride (PdCl₂),palladium(II) acetylacetonate (Pd(acac)₂), followed by drying,calcining, and reduction to elemental metal (see, e.g., Toebes et al.,“Synthesis of supported palladium catalysts,” Journal of MolecularCatalysis A: Chemical 173 (2001) 75-98).

General Procedures for Preparation of Catalysts for Oxidation Reaction(Oxidative “Nano-on-Nano-on-Micro” Particles or “NNm”™ Particles)

To prepare an oxidative catalytically active particle, a dispersion ofoxidative composite nanoparticles may be applied to porous, micron-sizedAl₂O₃, which may be purchased, for example, from companies such asRhodia or Sasol. The porous, micron-sized, Al₂O₃ powders may bestabilized with a small percentage of lanthanum and/or lanthanum oxide(about 2% to about 4% La). One commercial alumina powder suitable foruse is MI-386, which may be purchased from Grace Davison or Rhodia. Theusable surface for this powder, defined by pore sizes greater than 0.28μm, is approximately 2.8 m²/g. The ratio of composite nanoparticles usedto micron-sized carrier particles used may be from about 3:100 to about10:100, about 5:100 to about 8:100, or about 6.5:100, in terms of(weight of composite nanoparticle):(weight of micron carrier particle).In some embodiments, about 8 grams of composite nanoparticles may beused with about 122 grams of carrier micro-particles. The aqueousdispersion of composite nanoparticles may be applied in small portions(such as by dripping or other methods) to the micron-sized powder untilthe point of incipient wetness, producing a material similar to dampsand as described below.

In some instances, the sizes of the nano-sized oxidative catalysts, forexample Pd, Pt, or Pt/Pd are about 1 nm and the sizes of the nano-sizedAl₂O₃ are about 10 nm. In some instances, the sizes of the nano-sizedoxidative catalysts are approximately 1 nm or less and the sizes of thenano-sized Al₂O₃ are approximately 10 nm or less. In some instances, Pdis used as the oxidative catalyst and the weight ratio of nano-sizedPd:nano-sized aluminum oxide is about 5%:95%. In some instances, theweight percentage of nano-sized Pd is between about 5% to about 20% ofnano-sized Pd on nano-sized aluminum oxide. The nano-on-nano materialthat contains nano-sized Pd on nano-sized Al₂O₃ shows a dark blackcolor. In some instances, Pt is used as the oxidative catalyst and theweight ratio of nano-sized Pt:nano-sized aluminum oxide is about40%:60%. In some instances, a mixture of Pt and Pd is used as theoxidative catalyst. In some embodiments, the weight ratio of nano-sizedPt/Pd:nano-sized aluminum oxide is about 5%:95%. In some embodiments,the weight ratio of nano-sized Pt/Pd:nano-sized aluminum oxide is about10%:90%. In some embodiments, the weight ratio of nano-sizedPt/Pd:nano-sized aluminum oxide is about 20%:80%. In some embodiments,the weight ratio of nano-sized Pt/Pd:nano-sized aluminum oxide is about30%:70%. In some embodiments, the weight ratio of nano-sizedPt/Pd:nano-sized aluminum oxide is about 40%:60%.

A solution containing dispersed nano-on-nano material can be preparedusing a sonication process to disperse nano-on-nano particles into waterwith pH ˜4. Subsequently, 100 g of micron-sized MI-386 Al₂O₃ is put intoa mixer, and a 100 g dispersion containing the nano-on-nano material isinjected into the mixing aluminum oxide. This process is referred to asthe incipient wetness process or method.

Next, the wet powder is dried at 60° C. in a convection oven overnightuntil it is fully dried. Once the powder is dried, calcination isperformed. The dried powder from the previous step, that is, thenanomaterials on the micron-sized material, is baked at 550° C. for twohours under ambient air conditions. During the calcination, thesurfactant is burned off and the nanomaterials are glued or fixed ontothe surface of the micron-sized materials or onto the surface of thepores of the micron-materials. One explanation for why the nanomaterialscan be glued or fixed more permanently onto the micron-sized materialduring the calcination is because oxygen-oxygen (O—O) bonds, oxide-oxidebonds, or covalent bonds are formed during the calcination step. Theoxide-oxide bonds can be formed between the nanomaterials (nano-on-nanowith nano-on-nano, nano-on-nano with nano-sized aluminum oxide, andnano-sized aluminum oxide with nano-sized aluminum oxide), between thenanomaterials and the micron-sized materials, and between themicron-sized materials themselves. The oxide-oxide bond formation issometimes referred to as a solid state reaction. At this stage, thematerial produced contains a micron-sized particle having nano-on-nanoand nano-sized Al₂O₃ randomly distributed on the surface.

The oxidative NNm™ particles may contain from about 0.5% to about 5%palladium by weight, or in another embodiment from about 1% to 3% byweight, or in another embodiment, about 1.2% to 2.5% by weight, of thetotal mass of the NNm™ particle. The oxidative NNm™ particles maycontain from about 1% to about 6% platinum by weight, of the total massof the NNm™ particle. The oxidative NNm™ particles may contain fromabout 1% to about 6% platinum/palladium by weight, or in anotherembodiment, about 2% to 3% by weight, of the total mass of the NNm™particle.

General Procedures for Preparation of Catalysts for Reduction Reaction(Reductive “Nano-on-Nano-on-Micro” Particles or “NNm”™ Particles)

To prepare a reductive catalytically active particle, a dispersion ofreductive composite nanoparticles may be applied to porous, micron-sizedcerium oxide, which may be purchased, for example, from companies suchas Rhodia-Solvay. One commercial cerium oxide powder suitable for use isHSA5, HSA20, or a mixture thereof, available from Rhodia-Solvay. Themicron-sized cerium oxide may contain zirconium oxide. In someembodiments, the micron-sized cerium oxide is substantially free ofzirconium oxide. In other embodiments, the micron-sized cerium oxidecontains up to 100% zirconium oxide. In one embodiment, the reductivecomposite nanoparticle is rhodium.

The micron-sized carrier particles, impregnated with the compositereductive nanoparticles and nano-sized metal oxide, may then be dried(for example, at about 30° C. to about 95° C., preferably about 60° C.to about 70° C., at atmospheric pressure or at reduced pressure, such asfrom about 1 pascal to about 90,000 pascal). After drying, the particlesmay be calcined (at elevated temperatures, such as from 400° C. to about700° C., preferably about 500° C. to about 600° C., more preferably atabout 540° C. to about 560° C., still more preferably at about 550° C.to about 560° C., or at about 550° C.; at atmospheric pressure or atreduced pressure, for example, from about 1 pascal to about 90,000pascal, in ambient atmosphere or under an inert atmosphere such asnitrogen or argon) to yield the composite micro/nanoparticles, alsoreferred to as nano-on-nano-on-micro particles, or NNm™ particles. Thedrying step may be performed before the calcining step to remove waterprior to heating at the higher calcining temperatures; this avoidsboiling of the water, which would disrupt the impregnated nanoparticles,which are lodged in the pores of the micron-sized carrier.

The catalyst for reduction reactions can be made using a proceduresimilar to that employed for production of the catalyst for oxidationreactions. The nano-on-nano materials, for example nano-sized Rh onnano-sized cerium oxide, can be prepared using the method describedabove. In some instances, the sizes of the nano-sized Rh are about 1 nmand the sizes of the nano-sized cerium oxide are about 10 nm. In someinstances, the sizes of the nano-sized Rh are approximately 1 nm or lessand the sizes of the nano-sized cerium oxide are approximately 10 nm orless. In some embodiments, the weight ratio of nano-sized Rh:nano-sizedcerium oxide is from 1%:99% to 20%:80%. In some embodiments, the weightratio of nano-sized Rh:nano-sized cerium oxide is from 2%:98% to15%:85%. In some embodiments, the weight ratio of nano-sizedRh:nano-sized cerium oxide is from 3%:97% to 10%:90%. In someembodiments, the weight ratio of nano-sized Rh:nano-sized cerium oxideis from 4%:96% to 6%:94%. In some embodiments, the weight ratio ofnano-sized Rh:nano-sized cerium oxide is about 5%:95%.

Next, calcination can be performed. The dried powder from the previousstep, that is, the nanomaterials on the micron-sized material, can bebaked at 550° C. for two hours under ambient air conditions. During thecalcination step, the surfactant is evaporated and the nanomaterials areglued or fixed onto the surface of the micron-sized materials or thesurface of the pores of the micron-sized materials. At this stage, thematerial produced (a catalytic active material) contains a micron-sizedparticle (micron-sized cerium oxide) having nano-on-nano (such asnano-sized Rh on nano-sized cerium oxide) and nano-sized cerium oxiderandomly distributed on the surface.

The reductive NNm™ particles may contain from about 0.1% to 1.0% rhodiumby weight, or in another embodiment from about 0.2% to 0.5% by weight,or in another embodiment, about 0.3% by weight, or in anotherembodiment, about 0.4% by weight, of the total mass of the NNm™particle. The NNm™ particles can then be used for formulations forcoating substrates, where the coated substrates may be used in catalyticconverters.

General Procedures for Preparation of Catalysts for PNA Material (PNA“Nano-on-Nano-on-Micro” Particles or “NNm”™ Particles)

To prepare a PNA particle, a dispersion of PNA composite nanoparticlesmay be applied to porous, micron-sized cerium oxide, which may bepurchased, for example, from companies such as Rhodia-Solvay. Onecommercial cerium oxide powder suitable for use is HSA5, HSA20, or amixture thereof, available from Rhodia-Solvay. The micron-sized ceriumoxide may further comprise zirconium oxide. In some embodiments, themicron-sized cerium oxide is substantially free of zirconium oxide. Inother embodiments, the micron-sized cerium oxide contains up to 100%zirconium oxide. In addition, the micron-sized cerium oxide may furthercomprise lanthanum and/or lanthanum oxide. In some embodiments, themicro-sized cerium oxide may further comprise both zirconium oxide andlanthanum oxide. In some embodiments, the micron-sized cerium oxide mayfurther comprise yttrium oxide. Accordingly, the micron-sized ceriumoxide can be cerium oxide, cerium-zirconium oxide, cerium-lanthanumoxide, cerium-yttrium oxide, cerium-zirconium-lanthanum oxide,cerium-zirconium-yttrium oxide, cerium-lanthanum-yttrium oxide,cerium-zirconium-lanthanum-yttrium oxide, or a combination thereof. Insome embodiments, the nano-sized cerium oxide particles contain 40-90 wt% cerium oxide, 5-60 wt % zirconium oxide, 1-15 wt % lanthanum oxide,and/or 1-10 wt % yttrium oxide. In one embodiment, the micro-sizedcerium oxide contains 86 wt. % cerium oxide, 10 wt. % zirconium oxide;and 4 wt. % lanthanum and/or lanthanum oxide. In another embodiment, thecerium oxide particles contain 40 wt % cerium oxide, 50 wt % zirconiumoxide, 5 wt % lanthanum oxide, and 5 wt % yttrium oxide. In oneembodiment, the PGM of the PNA composite nanoparticle is palladium. Inone embodiment, the PGM of the PNA composite nanoparticle is ruthenium.The ruthenium of the PNA composite nanoparticle can be ruthenium oxide.

The micron-sized carrier particles, impregnated with the composite PNAnanoparticles and nano-sized metal oxide, may then be dried (forexample, at about 30° C. to about 95° C., preferably about 60° C. toabout 70° C., at atmospheric pressure or at reduced pressure, such asfrom about 1 pascal to about 90,000 pascal). After drying, the particlesmay be calcined (at elevated temperatures, such as from 400° C. to about700° C., preferably about 500° C. to about 600° C., more preferably atabout 540° C. to about 560° C., still more preferably at about 550° C.to about 560° C., or at about 550° C.; at atmospheric pressure or atreduced pressure, for example, from about 1 pascal to about 90,000pascal, in ambient atmosphere or under an inert atmosphere such asnitrogen or argon) to yield the composite micro/nanoparticles, alsoreferred to as nano-on-nano-on-micro particles, or NNm™ particles. Thedrying step may be performed before the calcining step to remove waterprior to heating at the higher calcining temperatures; this avoidsboiling of the water, which would disrupt the impregnated nanoparticles,which are lodged in the pores of the micron-sized carrier.

The PNA material can be made using a procedure similar to that employedfor production of the catalyst for oxidation reactions. The nano-on-nanomaterials, for example nano-sized Pd, Ru, or ruthenium oxide onnano-sized cerium oxide, can be prepared using the method describedabove. In some instances, the sizes of the nano-sized Pd, Ru, orruthenium oxide are from about 1 nm to about 5 nm and the sizes of thenano-sized cerium oxide are from about 5 nm to about 10 nm. In someinstances, the sizes of the nano-sized Pd, Ru, or ruthenium oxide areapproximately 1 nm or less and the sizes of the nano-sized cerium oxideare approximately 10 nm or less. In some embodiments, the weight ratioof nano-sized Pd, Ru, or ruthenium oxide:nano-sized cerium oxide is from1%:99% to 40%:60%. In some embodiments, the weight ratio of nano-sizedPd, Ru, or ruthenium oxide:nano-sized cerium oxide is from 5%:95% to20%:80%. In some embodiments, the weight ratio of nano-sized Pd, Ru, orruthenium oxide:nano-sized cerium oxide is from 8%:92% to 12%:88%. Insome embodiments, the weight ratio of nano-sized Pd, Ru, or rutheniumoxide:nano-sized cerium oxide is from 9%:91% to 11%:89%. In someembodiments, the weight ratio of nano-sized Pd, Ru, or rutheniumoxide:nano-sized cerium oxide is about 10%:90%.

Next, calcination can be performed. The dried powder from the previousstep, that is, the nanomaterials on the micron-sized material, can bebaked at 550° C. for two hours under ambient air conditions. During thecalcination step, the surfactant is evaporated and the nanomaterials areglued or fixed onto the surface of the micron-sized materials or thesurface of the pores of the micron-sized materials. At this stage, thematerial produced (a catalytic active material) contains a micron-sizedparticle (micron-sized cerium oxide) having nano-on-nano (such asnano-sized Pd, Ru, or ruthenium oxide on nano-sized cerium oxide) andnano-sized cerium oxide randomly distributed on the surface.

The PNA NNm™ particles may contain from about 0.1% to 6% Pd, Ru, orruthenium oxide by weight, or in another embodiment from about 0.5% to3.5% by weight, or in another embodiment, about 1% to about 2.5% byweight, or in another embodiment about 2% to about 3% by weight, or inanother embodiment, about 2.5% by weight, of the total mass of the NNm™particle. The NNm™ particles can then be used for formulations forcoating substrates, where the coated substrates may be used in catalyticconverters.

Porous Materials for Use in “Nano-on-Nano-in-Micro” Particles (“NNiM”Particles)

Porous materials, production of porous materials, micron-sized particlescomprising composite nanoparticles and a porous carrier(“Nano-on-Nano-in-Micro” particles or “NNiM” particles), and productionof micron-sized particles comprising composite nanoparticles and aporous carrier (“Nano-on-Nano-in-Micro” particles or “NNiM” particles)are described in the co-owned U.S. Provisional Patent Application No.61/881,337, filed on Sep. 23, 2013, U.S. patent application Ser. No.14/494,156 (U.S. Patent Appl. Publ. 2015/0140317), and InternationalPatent Application No. PCT/US2014/057036 (WO 2015/042598), thedisclosures of which are hereby incorporated by reference in theirentirety.

Generally, a preferred porous material is a material that contains alarge number of interconnected pores, holes, channels, or pits, with anaverage pore, hole, channel, or pit width (diameter) ranging from 1 nmto about 200 nm, or about 1 nm to about 100 nm, or about 2 nm to about50 nm, or about 3 nm to about 25 nm. In some embodiments, the porousmaterial has a mean pore, hole, channel, or pit width (diameter) of lessthan about 1 nm, while in some embodiments, a porous carrier has a meanpore, hole, channel, or pit width (diameter) of greater than about 100nm. In some embodiments, the porous material has an average pore surfacearea in a range of about 50 m²/g to about 500 m²/g. In some embodiments,the porous material has an average pore surface area in a range of about100 m²/g to about 400 m²/g. In some embodiments, a porous material hasan average pore surface area in a range of about 150 m²/g to about 300m²/g. In some embodiments, the porous material has an average poresurface area of less than about 50 m²/g. In some embodiments, the porousmaterial has an average pore surface area of greater than about 200m²/g. In some embodiments, the porous material has an average poresurface area of greater than about 300 m²/g. In some embodiments, aporous material has an average pore surface area of about 200 m²/g. Insome embodiments, a porous material has an average pore surface area ofabout 300 m²/g.

In some embodiments, the porous material may comprise porous metaloxide, such as aluminum oxide or cerium oxide. In some embodiments, aporous material may comprise an organic polymer, such as polymerizedresorcinol. In some embodiments, the porous material may compriseamorphous carbon. In some embodiments, the porous material may comprisesilica. In some embodiments, a porous material may be porous ceramic. Insome embodiments, the porous material may comprise a mixture of two ormore different types of interspersed porous materials, for example, amixture of aluminum oxide and polymerized resorcinol. In someembodiments, the porous carrier may comprise aluminum oxide after aspacer material has been removed. For example, in some embodiments, acomposite material may be formed with interspersed aluminum oxide andpolymerized resorcinol, and the polymerized resorcinol is removed, forexample, by calcination, resulting in a porous carrier. In anotherembodiment, a composite material may be formed with interspersedaluminum oxide and carbon black, and the carbon black is removed, forexample, by calcination, resulting in a porous carrier.

In some embodiments, the porous material is a micron-sized particle,with an average size between about 1 micron and about 100 microns,between about 1 micron and about 10 microns, between about 3 microns andabout 7 microns, or between about 4 microns and about 6 microns. Inother embodiments, the porous material may be particles larger thanabout 7 microns. In some embodiments, the porous material may not be inthe form of particles, but a continuous material.

The porous materials may allow gases and fluids to slowly flowthroughout the porous material via the interconnected channels, beingexposed to the high surface area of the porous material. The porousmaterials can therefore serve as an excellent carrier material forembedding particles in which high surface area exposure is desirable,such as catalytic nanoparticles, as described below.

Production of Porous Materials for Use in “Nano-on-Nano-in-Micro”Particles (“NNiM” Particles)

A catalyst or PNA material may be formed using a porous material. Thisporous material includes, for example, nanoparticles embedded within theporous structure of the material. This can include nano-on-nanoparticles (composite nanoparticles) embedded into a porous carrierformed around the nano-on-nano particles. Nanoparticles embedded in aporous carrier can refer to the configuration of the nanoparticles inthe porous carrier resulting when the porous carrier is formed aroundthe nanoparticles, generally by using the methods described herein. Thatis, the resulting structure contains nanoparticles with a scaffolding ofporous carrier built up around or surrounding the nanoparticles. Theporous carrier encompasses the nanoparticles, while at the same time, byvirtue of its porosity, the porous carrier permits external gases tocontact the embedded nanoparticles.

PNA nano-on-nano particles can be produced, where the PGM can comprisepalladium, ruthenium, or ruthenium oxide, and the support nanoparticlescan comprise cerium oxide, cerium-zirconium oxide, cerium-lanthanumoxide, cerium-yttrium oxide, cerium-zirconium-lanthanum oxide,cerium-zirconium-yttrium oxide, cerium-lanthanum-yttrium oxide, orcerium-zirconium-lanthanum-yttrium oxide. Oxidative nano-on-nanoparticles can be produced, where the catalytic nanoparticle can compriseplatinum, palladium, or platinum/palladium alloy, and the supportnanoparticle can comprise aluminum oxide. Reductive nano-on-nanoparticles can be produced, where the catalytic nanoparticle can compriserhodium, and the support nanoparticle can comprise cerium oxide. Thesupport nanoparticle can comprise cerium oxide, cerium-zirconium oxide,cerium-lanthanum oxide, cerium-yttrium oxide, cerium-zirconium-lanthanumoxide, cerium-zirconium-yttrium oxide, cerium-lanthanum-yttrium oxide,or cerium-zirconium-lanthanum-yttrium oxide.

In some embodiments, the porous structure comprises alumina or ceriumoxide. In some embodiments, the cerium oxide can include zirconiumoxide, lanthanum, lanthanum oxide, yttrium oxide or a combinationthereof. In some embodiments, the nano-sized cerium oxide particlescontain 40-90 wt % cerium oxide, 5-60 wt % zirconium oxide, 1-15 wt %lanthanum oxide, and/or 1-10 wt % yttrium oxide. In one embodiment, thecerium oxide particles contain 86 wt % cerium oxide, 10 wt % zirconiumoxide, and 4 wt % lanthanum and/or lanthanum oxide. In anotherembodiment, the cerium oxide particles contain 40 wt % cerium oxide, 50wt % zirconium oxide, 5 wt % lanthanum oxide, and 5 wt % yttrium oxide.

The porous materials with embedded nano-on-nano particles within theporous structure of the material, where the porous structure comprisesalumina, or where the porous structure comprises ceria, or where theporous structure comprises cerium-zirconium oxide,cerium-zirconium-lanthanum oxide, or cerium-zirconium-lanthanum-yttriumoxide, can be prepared as follows. Alumina porous structures may beformed, for example, by the methods described in U.S. Pat. No.3,520,654, the disclosure of which is hereby incorporated by referencein its entirety. In some embodiments, a sodium aluminate solution,prepared by dissolving sodium oxide and aluminum oxide in water, can betreated with sulfuric acid or aluminum sulfate to reduce the pH to arange of about 4.5 to about 7. The decrease in pH results in aprecipitation of porous hydrous alumina which may be spray dried,washed, and flash dried, resulting in a porous alumina material.Optionally, the porous alumina material may be stabilized with silica,as described in EP0105435 A2, the disclosure of which is herebyincorporated by reference in its entirety. A sodium aluminate solutioncan be added to an aluminum sulfate solution, forming a mixture with apH of about 8.0. An alkaline metal silicate solution, such as a sodiumsilicate solution, can be slowly added to the mixture, resulting in theprecipitation of a silica-stabilized porous alumina material.

A porous material may also be generated by co-precipitating aluminumoxide nanoparticles and amorphous carbon particles, such as carbonblack. Upon drying and calcination of the precipitate in an ambient oroxygenated environment, the amorphous carbon is exhausted, that is,burned off. Simultaneously, the heat from the calcination process causesthe aluminum oxide nanoparticles to sinter together, resulting in poresthroughout the precipitated aluminum oxide where the carbon black onceappeared in the structure. In some embodiments, aluminum oxidenanoparticles can be suspended in ethanol, water, or a mix of ethanoland water. In some embodiments, dispersant, such as DisperBYK®-145 fromBYK (DisperBYK is a registered trademark of BYK-Chemie GmbH LLC, Wesel,Germany for chemicals for use as dispersing and wetting agents) may beadded to the aluminum oxide nanoparticle suspension. Carbon black withan average grain size ranging from about 1 nm to about 200 nm, or about20 nm to about 100 nm, or about 20 nm to about 50 nm, or about 35 nm,may be added to the aluminum oxide suspension. In some embodiments,sufficient carbon black is added to obtain a pore surface area of about50 m²/g to about 500 m²/g should be used, such as about 50 m²/g, about100 m²/g, about 150 m²/g, about 200 m²/g, about 250 m²/g, about 300m²/g, about 350 m²/g, about 400 m²/g, about 450 m²/g, or about 500 m²/g.The pH of the resulting mixture can be adjusted to a range of about 2 toabout 7, such as a pH of between about 3 and about 5, preferably a pH ofabout 4, allowing the particles to precipitate. In some embodiments, theprecipitant can be dried, for example by warming the precipitant (forexample, at about 30° C. to about 95° C., preferably about 60° C. toabout 70° C., at atmospheric pressure or at reduced pressure such asfrom about 1 pascal to about 90,000 pascal). Alternatively, in someembodiments, the precipitant may be freeze-dried.

After drying, the material may then be calcined (at elevatedtemperatures, such as from 400° C. to about 700° C., preferably about500° C. to about 600° C., more preferably at about 540° C. to about 560°C., still more preferably at about 550° C. to about 560° C., or at about550° C.; at atmospheric pressure or at reduced pressure, for example,from about 1 pascal to about 90,000 pascal, in ambient atmosphere). Thecalcination process causes the carbon black to substantially burn awayand the aluminum oxide nanoparticles sinter together, yielding a porousaluminum oxide material.

In other embodiments, a porous material may also be generated byco-precipitating cerium oxide nanoparticles and amorphous carbonparticles, such as carbon black. Upon drying and calcination of theprecipitate in an ambient or oxygenated environment, the amorphouscarbon is exhausted, that is, burned off. Simultaneously, the heat fromthe calcination process causes the cerium oxide nanoparticles to sintertogether, resulting in pores throughout the precipitated cerium oxidewhere the carbon black once appeared in the structure. In someembodiments, cerium oxide nanoparticles can be suspended in ethanol,water, or a mix of ethanol and water. In some embodiments, dispersant,such as DisperBYK®-145 from BYK (DisperBYK is a registered trademark ofBYK-Chemie GmbH LLC, Wesel, Germany for chemicals for use as dispersingand wetting agents) may be added to the cerium oxide nanoparticlesuspension. Carbon black with an average grain size ranging from about 1nm to about 200 nm, or about 20 nm to about 100 nm, or about 20 nm toabout 50 nm, or about 35 nm, may be added to the cerium oxidesuspension. In some embodiments, sufficient carbon black is added toobtain a pore surface area of about 50 m²/g to about 500 m²/g should beused, such as about 50 m²/g, about 100 m²/g, about 150 m²/g, about 200m²/g, about 250 m²/g, about 300 m²/g, about 350 m²/g, about 400 m²/g,about 450 m²/g, or about 500 m²/g. The pH of the resulting mixture canbe adjusted to a range of about 2 to about 7, such as a pH of betweenabout 3 and about 5, preferably a pH of about 4, allowing the particlesto precipitate. In some embodiments, the precipitant can be dried, forexample by warming the precipitant (for example, at about 30° C. toabout 95° C., preferably about 60° C. to about 70° C., at atmosphericpressure or at reduced pressure such as from about 1 pascal to about90,000 pascal). Alternatively, in some embodiments, the precipitant maybe freeze-dried.

After drying, the material may then be calcined (at elevatedtemperatures, such as from 400° C. to about 700° C., preferably about500° C. to about 600° C., more preferably at about 540° C. to about 560°C., still more preferably at about 550° C. to about 560° C., or at about550° C.; at atmospheric pressure or at reduced pressure, for example,from about 1 pascal to about 90,000 pascal, in ambient atmosphere). Thecalcination process causes the carbon black to substantially burn awayand the cerium oxide nanoparticles sinter together, yielding a porouscerium oxide material.

In some embodiments, a porous material may be made using the sol-gelprocess. For example, a sol-gel precursor to an alumina porous materialmay be formed by reacting aluminum chloride with propylene oxide.Propylene oxide can be added to a solution of aluminum chloridedissolved in a mixture of ethanol and water, which forms a porousmaterial that may be dried and calcined. In some embodiments,epichlorohydrin may be used in place of propylene oxide. As anotherexample, a sol-gel precursor to a ceria porous material may be formed byreacting cerium nitrate with resorcinol and formaldehyde. Other methodsof producing a porous material using the sol-gel method known in the artmay also be used, for example, a porous material formed using thesol-gel process may be also be formed using tetraethyl orthosilicate.

In some embodiments, the porous material may be formed by mixing theprecursors of a combustible gel with the precursors of a metal oxidematerial prior to polymerization of the gel, allowing the polymerizationof the gel, drying the composite material, and calcining the compositematerial, thereby exhausting the organic gel components. In someembodiments, a gel activation solution comprising a mixture offormaldehyde and propylene oxide can be mixed with a gel monomersolution comprising a mixture of aluminum chloride and resorcinol. Uponmixing of the gel activation solution and the gel monomer solution, acombustible organic gel component forms as a result of the mixing offormaldehyde and resorcinol, and a non-combustible inorganic metal oxidematerial forms as a result of mixing the propylene oxide and aluminumchloride. The resulting composite material can be dried and calcined,causing the combustible organic gel component to burn away, resulting ina porous metal oxide material (aluminum oxide). In another embodiment, asolution of formaldehyde can be reacted with a solution of resorcinoland cerium nitrate. The resulting material can be dried and calcined,causing the combustible organic gel component to burn away, resulting ina porous metal oxide material (cerium oxide). The resulting material canbe dried and calcined, causing the combustible organic gel component toburn away, resulting in a porous metal oxide material (cerium oxide). Inyet further embodiments, a solution of formaldehyde can be reacted witha solution of resorcinol, cerium nitrate, and one or more of zirconiumoxynitrate, lanthanum acetate, and/or yttrium nitrate as appropriate toform cerium-zirconium oxide, cerium-zirconium-lanthanum oxide, orcerium-zirconium-lanthanum-yttrium oxide. The resulting material can bedried and calcined, causing the combustible organic gel component toburn away, resulting in a porous metal oxide material (cerium-zirconiumoxide, cerium-zirconium-lanthanum oxide, orcerium-zirconium-lanthanum-yttrium oxide).

In some embodiments, the gel activation solution may be prepared bymixing aqueous formaldehyde and propylene oxide. The formaldehyde ispreferably in an aqueous solution. In some embodiments, theconcentration of the aqueous formaldehyde solution is about 5 wt % toabout 50 wt % formaldehyde, about 20 wt % to about 40 wt % formaldehyde,or about 30 wt % to about 40 wt % formaldehyde. Preferably, the aqueousformaldehyde is about 37 wt % formaldehyde. In some embodiments, theaqueous formaldehyde may contain about 5 wt % to about 15 wt % methanolto stabilize the formaldehyde in solution. The aqueous formaldehyde canbe added in a range of about 25% to about 50% of the final weight of thegel activation solution, with the remainder being propylene oxide.Preferably, the gel activation solution comprises 37.5 wt % of theaqueous formaldehyde solution (which itself comprises 37 wt %formaldehyde) and 62.5 wt % propylene oxide, resulting in a finalformaldehyde concentration of about 14 wt % of the final gel activationsolution.

Separately from the gel activation solution, a gel monomer solution maybe produced by dissolving aluminum chloride in a mixture of resorcinoland ethanol. Resorcinol can be added at a range of about 2 wt % to about10 wt %, with about 5 wt % being a typical value. Aluminum chloride canbe added at a range of about 0.8 wt % to about 5 wt %, with about 1.6 wt% being a typical value.

The gel activation solution and gel monomer solution can be mixedtogether at a ratio at about 1:1 in terms of (weight of gel activationsolution):(weight of gel monomer solution). The final mixture may thenbe dried (for example, at about 30° C. to about 95° C., preferably about50° C. to about 60° C., at atmospheric pressure or at reduced pressuresuch as from about 1 pascal to about 90,000 pascal, for about one day toabout 5 days, or for about 2 days to about 3 days). After drying, thematerial may then be calcined (at elevated temperatures, such as from400° C. to about 700° C., preferably about 500° C. to about 600° C.,more preferably at about 540° C. to about 560° C., still more preferablyat about 550° C. to about 560° C., or at about 550° C.; at atmosphericpressure or at reduced pressure, for example, from about 1 pascal toabout 90,000 pascal, in ambient atmosphere, for about 12 hours to about2 days, or about 16 hours to about 24 hours) to burn off the combustibleorganic gel component and yield a porous aluminum oxide carrier.

Gel monomer solutions can be prepared with cerium nitrate, zirconiumoxynitrate, lanthanum acetate, and/or yttrium nitrate in a processsimilar to that described above, for preparation of porous cerium oxide,cerium-zirconium oxide, cerium-lanthanum oxide, cerium-yttrium oxide,cerium-zirconium-lanthanum oxide, cerium-zirconium-yttrium oxide,cerium-lanthanum-yttrium oxide, or cerium-zirconium-lanthanum-yttriumoxide carrier.

The porous materials prepared above are then ground or milled intomicron-sized particles.

Nano-on-nano-in-micro (“NNiM”™) materials are prepared by mixingnano-on-nano (NN) particles into the precursors to the porous materials,for example, by using a portion of NN particles when mixing togethernanoparticles with amorphous carbon, or by mixing NN particles into thesol-gel solution, followed by preparation of the porous material asdescribed above. After grinding or milling the porous material withembedded NN particles into micron-sized particles (to form “NNiM”™materials), the resulting material can then be used in an oxidativewashcoat, a reductive washcoat, a PNA washcoat, or a combined washcoatof any of the oxidative, reductive, and PNA washcoats. The amount of NNparticles added is guided by the desired loading of PGM metal in thefinal NNiM material.

Oxidative NNiM material can be formed, where the nano-on-nano compositenanoparticles comprise a platinum catalytic nanoparticle disposed on analuminum oxide support particle; where the nano-on-nano compositenanoparticles comprise a palladium catalytic nanoparticle disposed on analuminum oxide support particle; or where the nano-on-nano compositenanoparticles comprise a platinum/palladium alloy catalytic nanoparticledisposed on an aluminum oxide support particle; and one or more of thoseNN particles is then embedded in a porous carrier formed of aluminumoxide, which is ground or milled into micron-sized particles. ReductiveNNiM material can be formed, where the nano-on-nano compositenanoparticles comprise a rhodium catalytic nanoparticle disposed on acerium oxide support particle; where the nano-on-nano compositenanoparticles comprise a rhodium catalytic nanoparticle disposed on acerium-zirconium oxide support particle; where the nano-on-nanocomposite nanoparticles comprise a rhodium catalytic nanoparticledisposed on a cerium-zirconium-lanthanum oxide support particle; orwhere the nano-on-nano composite nanoparticles comprise a rhodiumcatalytic nanoparticle disposed on a cerium-zirconium-lanthanum-yttriumoxide support particle; and one or more of those NN particles is thenembedded in a porous carrier formed of porous cerium oxide,cerium-zirconium oxide, cerium-lanthanum oxide, cerium-yttrium oxide,cerium-zirconium-lanthanum oxide, cerium-zirconium-yttrium oxide,cerium-lanthanum-yttrium oxide, or cerium-zirconium-lanthanum-yttriumoxide carrier, which is ground or milled into micron-sized particles.PNA NNiM material can be formed, where the nano-on-nano compositenanoparticles comprise a palladium nanoparticle disposed on a ceriumoxide support particle; where the nano-on-nano composite nanoparticlescomprise a palladium nanoparticle disposed on a cerium-zirconium oxidesupport particle; where the nano-on-nano composite nanoparticlescomprise a palladium nanoparticle disposed on acerium-zirconium-lanthanum oxide support particle; or where thenano-on-nano composite nanoparticles comprise a palladium nanoparticledisposed on a cerium-zirconium-lanthanum-yttrium oxide support particle;and one or more of those NN particles is then embedded in a porouscarrier formed of aluminum oxide, cerium oxide, cerium-zirconium oxide,cerium-lanthanum oxide, cerium-yttrium oxide, cerium-zirconium-lanthanumoxide, cerium-zirconium-yttrium oxide, cerium-lanthanum-yttrium oxide,or cerium-zirconium-lanthanum-yttrium oxide, which is ground or milledinto micron-sized particles. PNA NNiM material can be formed, where thenano-on-nano composite nanoparticles comprise a ruthenium or rutheniumoxide nanoparticle disposed on a cerium oxide support particle; wherethe nano-on-nano composite nanoparticles comprise a ruthenium orruthenium oxide nanoparticle disposed on a cerium-zirconium oxidesupport particle; where the nano-on-nano composite nanoparticlescomprise a ruthenium or ruthenium oxide nanoparticle disposed on acerium-zirconium-lanthanum oxide support particle; or where thenano-on-nano composite nanoparticles comprise a ruthenium or rutheniumoxide nanoparticle disposed on a cerium-zirconium-lanthanum-yttriumoxide support particle; and one or more of those NN particles is thenembedded in a porous carrier formed of aluminum oxide, cerium oxide,cerium-zirconium oxide, cerium-lanthanum oxide, cerium-yttrium oxide,cerium-zirconium-lanthanum oxide, cerium-zirconium-yttrium oxide,cerium-lanthanum-yttrium oxide, or cerium-zirconium-lanthanum-yttriumoxide, which is ground or milled into micron-sized particles Aluminumoxide porous material can also be used as the porous material in whichany of the foregoing rhodium-containing composite NN nanoparticles canbe embedded. The weight ratios of the NN particles used can be thosedescribed in the above NNm section. For example, the weight ratio ofnano-sized Pd, Ru, or ruthenium oxide:nano-sized cerium oxide can befrom 1%:99% to 40%:60%, from 5%:95% to 20%:80%, from 8%:92% to 12%:88%,from 9%:91% to 11%:89%, and 10%:90%.

Micron-Sized Particles Comprising Composite Nanoparticles and a PorousCarrier (“Nano-on-Nano-in-Micro” Particles or “NNiM” Particles)

Nanoparticles or composite nanoparticles produced by plasma productionor other methods may be embedded within a porous material to enhance thesurface area of catalytic components (this includes PNA componentsbecause PNA components include PGM which by its very nature iscatalytic). The porous material may then serve as a carrier for thecomposite nanoparticles, allowing gasses and fluids to slowly flowthroughout the porous material via the interconnected channels. The highporosity of the carrier results in a high surface area within thecarrier allowing increased contact of the gasses and fluids with theembedded catalytic components, such as composite nanoparticles.Embedding the composite nanoparticles within the porous carrier resultsin a distinct advantage over those technologies where catalyticallyactive nanoparticles are positioned on the surface of carriermicro-particles or do not penetrate as effectively into the pores of thesupport. When catalytically active nanoparticles are position on thesurface of carrier micro-particles, some catalytically activenanoparticles can become buried by other catalytically activenanoparticles, causing them to be inaccessible to target gases becauseof the limited exposed surface area. When the composite nanoparticlesare embedded within the porous carrier, however, gases can flow throughthe pores of the carrier to catalytically active components.

The porous carrier may contain any large number of interconnected pores,holes, channels, or pits, preferably with an average pore, hole,channel, or pit width (diameter) ranging from 1 nm to about 200 nm, orabout 1 nm to about 100 nm, or about 2 nm to about 50 nm, or about 3 nmto about 25 nm. In some embodiments, the porous carrier has a mean pore,hole, channel, or pit width (diameter) of less than about 1 nm, while insome embodiments, a porous carrier has a mean pore, hole, channel, orpit width (diameter) of greater than about 100 nm. In some embodiments,a porous material has an average pore surface area in a range of about50 m²/g to about 500 m²/g. In some embodiments, a porous material has anaverage pore surface area in a range of about 100 m²/g to about 400m²/g. In some embodiments, a porous material has an average pore surfacearea in a range of about 150 m²/g to about 300 m²/g. In someembodiments, a porous material has an average pore surface area of lessthan about 50 m²/g. In some embodiments, a porous material has anaverage pore surface area of greater than about 200 m²/g. In someembodiments, a porous material has an average pore surface area ofgreater than about 300 m²/g. In some embodiments, a porous material hasan average pore surface area of about 200 m²/g. In some embodiments, aporous material has an average pore surface area of about 300 m²/g.

A porous carrier embedded with nanoparticles can be formed with anyporous material. A porous carrier may include, but is not limited to,any gel produced by the sol-gel method, for example, alumina (Al₂O₃),cerium oxide, or silica aerogels as described herein. In someembodiments, the porous carrier may comprise a porous metal oxide, suchas aluminum oxide or cerium oxide. In some embodiments, a porous carriermay comprise an organic polymer, such as polymerized resorcinol. In someembodiments, the porous carrier may comprise amorphous carbon. In someembodiments, the porous carrier may comprise silica. In someembodiments, a porous carrier may be porous ceramic. In someembodiments, the porous carrier may comprise a mixture of two or moredifferent types of interspersed porous materials, for example, a mixtureof aluminum oxide and polymerized resorcinol.

In some embodiments, a carrier may comprise a combustible component, forexample amorphous carbon or a polymerized organic gel such aspolymerized resorcinol, and a non-combustible component, for example ametal oxide such as aluminum oxide. A catalytic material can includecomposite nanoparticles embedded in a carrier comprising a combustiblecomponent and a non-combustible component.

Catalytic and/or PNA particles, such as the catalytic nanoparticles orcatalytic and/or PNA composite nanoparticles described herein, areembedded within the porous carrier. This can be accomplished byincluding the catalytic and/or PNA particles in the mixture used to formthe porous carrier. In some embodiments, the catalytic and/or PNAparticles are evenly distributed throughout the porous carrier. In otherembodiments, the catalytic and/or PNA particles are clustered throughoutthe porous carrier. In some embodiments, platinum group metals compriseabout 0.001 wt % to about 10 wt % of the total catalytic and/or PNAmaterial (catalytic and/or PNA particles and porous carrier). Forexample, platinum group metals may comprise about 1 wt % to about 8 wt %of the total catalytic and/or PNA material (catalytic and/or PNAparticles and porous carrier). In some embodiments, platinum groupmetals may comprise less than about 10 wt %, less than about 8 wt %,less than about 6 wt %, less than about 4 wt %, less than about 2 wt %,or less than about 1 wt % of the total catalytic and/or PNA material(catalytic and/or PNA particles and porous carrier). In someembodiments, platinum group metals may comprise about 1 wt %, about 2 wt%, about 3 wt %, about 4 wt %, about 5 wt %, about 6 wt %, about 7 wt %,about 8 wt %, about 9 wt %, or about 10 wt % of the total catalyticand/or PNA material (catalytic and/or PNA particles and porous carrier).

In some embodiments, the catalytic and/or PNA nanoparticles comprise oneor more platinum group metals. In embodiments with two or more platinumgroup metals, the metals may be in any ratio. In some embodiments, thecatalytic nanoparticles comprise platinum group metal or metals, such asPt:Pd in about a 2:1 ratio to about 100:1 ratio by weight, or about 2:1to about 75:1 ratio by weight, or about 2:1 to about 50:1 ratio byweight, or about 2:1 to about 25:1 ratio by weight, or about 2:1 toabout 15:1 ratio by weight. In one embodiment, the catalyticnanoparticles comprise platinum group metal or metals, such as Pt:Pd inabout 2:1 ratio by weight.

The composite nanoparticles (nano-on-nano particles) embedded within aporous carrier may take the form of a powder to produce compositecatalytic micro-particles, referred to as “nano-on-nano-in-micron”particles or “NNiM” particles. In typical NNiM particles, a porousmaterial (or matrix) may be formed around and surround nanoparticles orcomposite nanoparticle produced by plasma production or other methods.The porous material can bridge together the surrounded nanoparticles orcomposite nanoparticles, thereby embedding the particles within thematrix. The porous material may then serve as a carrier for thecomposite nanoparticles, allowing gases and fluids to slowly flowthroughout the porous material (i.e., the interconnected bridges) viathe interconnected channels. The high porosity of the carrier results ina high surface area within the carrier allowing increased contact of thegases and fluids with the contained catalytic components, such ascomposite nanoparticles.

The micron-sized NNiM particles can have an average size between about 1micron and about 100 microns, such as between about 1 micron and about10 microns, between about 3 microns and about 7 microns, or betweenabout 4 microns and about 6 microns. The PGM particles may compriseabout 0.001 wt % to about 10 wt % of the total mass of the NNiM particle(catalytic and/or PNA particles and porous carrier). For example,platinum group metals may comprise about 1 wt % to about 8 wt % of thetotal mass of the NNiM particle (catalytic and/or PNA particles andporous carrier). In some embodiments, platinum group metals may compriseless than about 10 wt %, less than about 8 wt %, less than about 6 wt %,less than about 4 wt %, less than about 2 wt %, or less than about 1 wt% of the total mass of the NNiM particle (catalytic and/or PNA particlesand porous carrier). In some embodiments, platinum group metals maycomprise about 1 wt %, about 2 wt %, about 3 wt %, about 4 wt %, about 5wt %, about 6 wt %, about 7 wt %, about 8 wt %, about 9 wt %, or about10 wt % of the total mass of the NNiM particle (catalytic and/or PNAparticles and porous carrier).

NNiM particles may be used for any catalytic purpose or NO_(x) storagepurpose. For example, NNiM particles may be suspended in a liquid, forexample ethanol or water, which may catalyze dissolved compounds.Alternatively, the NNiM particles may be used as a solid state catalyst.For example, the NNiM particles can then be used in catalyticconverters.

Production of Micron-Sized Particles Comprising Composite Nanoparticlesand a Porous Carrier (“Nano-on-Nano-in-Micro” Particles or “NNiM”Particles)

In some embodiments, catalytic nanoparticles or composite nanoparticlescan be embedded in a porous carrier by forming a suspension or colloidof nanoparticles, and mixing the suspension or colloid of nanoparticleswith a porous material precursor solution. Upon solidification of theporous material with the mixture, such as by polymerization,precipitation, or freeze-drying, the porous material will form aroundthe nanoparticles, resulting in a catalytic material comprisingnanoparticles embedded in a porous carrier. In some embodiments, thecatalytic and/or PNA material is then processed, such as by grinding ormilling, into a micron-sized powder, resulting in NNiM particles.

Described below is the production of NNiM particles using a porousaluminum oxide carrier formed using a composite carrier comprising acombustible organic gel component and an aluminum oxide component,followed by drying and calcination. However, one skilled in the artwould understand any manner of porous carrier (such as cerium oxide)originating from soluble precursors may be used to produce catalytic(including PNA) material comprising composite nanoparticles embeddedwithin a porous carrier using the methods described herein.

For typical NNiM particles produced using a porous aluminum oxidecarrier formed using a composite carrier comprising a combustibleorganic gel component and an aluminum oxide component, the compositenanoparticles are initially dispersed in ethanol. In some embodiments,at least 95 vol % ethanol is used. In some embodiments, at least 99 vol% ethanol is used. In some embodiments, at least 99.9 vol % ethanol isused. Dispersants, surfactants, or mixtures thereof are typically addedto the ethanol before suspension of the composite nanoparticles. Asuitable surfactant includes DisperBYK®-145 from BYK-Chemie GmbH LLC,Wesel, which can be added in a range of about 2 wt % to about 12 wt %,with about 7 wt % being a typical value, and dodecylamine, which can beadded in a range of about 0.25 wt % to about 3 wt %, with about 1 wt %being a typical value. Preferably, both DisperBYK®-145 and dodecylamineare used at about 7 wt % and 1 wt %, respectively. In some embodiments,the mixture of ethanol, composite nanoparticles, and surfactants,dispersants, or mixtures thereof is sonicated to uniformly disperse thecomposite nanoparticles. The quantity of composite nanoparticlesparticles in the dispersion may be in the range of about 5 wt % to about20 wt %.

Separately from the composite nanoparticle suspension, a gel activationsolution is prepared by mixing formaldehyde and propylene oxide. Theformaldehyde is preferably in an aqueous solution. In some embodiments,the concentration of the aqueous formaldehyde solution is about 5 wt %to about 50 wt % formaldehyde, about 20 wt % to about 40 wt %formaldehyde, or about 30 wt % to about 40 wt % formaldehyde.Preferably, the aqueous formaldehyde is about 37 wt % formaldehyde. Insome embodiments, the aqueous formaldehyde may contain about 5 wt % toabout 15 wt % methanol to stabilize the formaldehyde in solution. Theaqueous formaldehyde solution can be added in a range of about 25% toabout 50% of the final weight of the gel activation solution, with theremainder being propylene oxide. Preferably, the gel activation solutioncomprises 37.5 wt % of the aqueous formaldehyde solution (which itselfcomprises 37 wt % formaldehyde) and 62.5 wt % propylene oxide, resultingin a final formaldehyde concentration of about 14 wt % of the final gelactivation solution.

Separately from the composite nanoparticle suspension and gel activationsolution, an aluminum chloride solution is produced by dissolvingaluminum chloride in a mixture of resorcinol and ethanol. Resorcinol canbe added at a range of about 10 wt % to about 30 wt %, with about 23 wt% being a typical value. Aluminum chloride can be added at a range ofabout 2 wt % to about 12 wt %, with about 7 wt % being a typical value.

The composite nanoparticle suspension, gel activation solution, andaluminum chloride solution can be mixed together at a ratio from ofabout 100:10:10 to about 100:40:40, or about 100:20:20 to about100:30:30, or about 100:25:25, in terms of (weight of compositenanoparticle suspension):(weight of gel activation solution):(weight ofaluminum chloride solution). The final mixture will begin to polymerizeinto a carrier embedded with composite nanoparticles. The carriercomprises a combustible component, an organic gel, and a non-combustiblecomponent, aluminum oxide. The resulting carrier may then be dried (forexample, at about 30° C. to about 95° C., preferably about 50° C. toabout 60° C., at atmospheric pressure or at reduced pressure such asfrom about 1 pascal to about 90,000 pascal, for about one day to about 5days, or for about 2 days to about 3 days). After drying, the resultingcarrier may then be calcined (at elevated temperatures, such as from400° C. to about 700° C., preferably about 500° C. to about 600° C.,more preferably at about 540° C. to about 560° C., still more preferablyat about 550° C. to about 560° C., or at about 550° C.; at atmosphericpressure or at reduced pressure, for example, from about 1 pascal toabout 90,000 pascal, in ambient atmosphere or under an inert atmospheresuch as nitrogen or argon), to yield a porous carrier comprisingcomposite catalytic nanoparticles and aluminate. When the compositecarrier is calcined under ambient atmosphere or other oxygenatedconditions, organic material, such as polymerized resorcinol,formaldehyde, or propylene oxide, is burnt off, resulting in asubstantially pure aluminum oxide porous carrier embedded with compositenanoparticles. If the composite carrier is calcined under an inertatmosphere, such as argon or nitrogen, the organic materials may becomesubstantially porous amorphous carbon interspersed with the porousaluminum oxide embedded with composite nanoparticles. The resultingporous carrier can be processed, such as by grinding or milling, into amicro-sized powder of NNiM particles.

In another embodiment, a composite catalytic nanoparticles may be mixedwith a dispersion comprising metal oxide nanoparticles, such as aluminumoxide nanoparticles, and amorphous carbon, such as carbon black. Thedispersed solid particles from resulting dispersed colloid may beseparated from the liquid by co-precipitation, dried, and calcined. Uponcalcination of the solid material in an ambient or oxygenatedenvironment, the amorphous carbon is exhausted. Simultaneously, the heatfrom the calcination process causes the aluminum oxide nanoparticles tosinter together, resulting in pores throughout the precipitated aluminumoxide.

In some embodiments, aluminum oxide nanoparticles can be suspended inethanol, water, or a mix of ethanol and water. Carbon black with anaverage grain size ranging from about 1 nm to about 200 nm, or about 20nm to about 100 nm, or about 20 nm to about 50 nm, or about 35 nm, maybe added to the aluminum oxide suspension. In some embodiments,sufficient carbon black to obtain a pore surface area of about 50 m²/gto about 500 m²/g should be used, such as about 50 m²/g, about 100 m²/g,about 150 m²/g, about 200 m²/g, about 250 m²/g, about 300 m²/g, about350 m²/g, about 400 m²/g, about 450 m²/g, or about 500 m²/g. Compositenanoparticles may be mixed into the dispersion comprising aluminum oxidenanoparticles and carbon black. In some embodiments, the compositenanoparticles are dispersed in a separate colloid, optionally withdispersants or surfactants, before being mixed with the dispersioncomprising aluminum oxide nanoparticles and carbon black. The pH of theresulting mixture can be adjusted to a range of about 2 to about 7, suchas a pH of between about 3 and about 5, preferably a pH of about 4,allowing the particles to precipitate. The precipitant can be dried (forexample, at about 30° C. to about 95° C., preferably about 50° C. toabout 70° C., at atmospheric pressure or at reduced pressure such asfrom about 1 pascal to about 90,000 pascal, for about one day to about 5days, or for about 2 days to about 3 days). After drying, the carriermay then be calcined (at elevated temperatures, such as from 400° C. toabout 700° C., preferably about 500° C. to about 600° C., morepreferably at about 540° C. to about 560° C., still more preferably atabout 550° C. to about 560° C., or at about 550° C.; at atmosphericpressure or at reduced pressure, for example, from about 1 pascal toabout 90,000 pascal, in ambient atmosphere). The calcination processcauses the carbon black to substantially burn away and the aluminumoxide nanoparticles sinter together, yielding a porous aluminum oxidecarrier embedded with composite nanoparticles.

The resulting carrier may be further processed, for example by grindingor milling, into micron-sized NNiM particles.

NNm™ and NNiM Particles with Inhibited Migration of Platinum GroupMetals

The NNm™ particles including micron-sized carrier particle bearingcomposite nanoparticles, where the composite nanoparticles are producedby methods described herein, are particularly advantageous for use incatalytic converter applications. The NNiM particles, including thosemade using a porous carrier and composite nanoparticles, where thecarrier is produced by methods described herein and compositenanoparticles produced under reducing conditions, are also particularlyadvantageous for use in catalytic converter applications. The platinumgroup metal of the catalytic and/or PNA nanoparticle has a greateraffinity for the partially reduced surface of the support nanoparticlethan for the surface of the micron-sized carrier particles. Thus, atelevated temperatures, neighboring PGM nanoparticles bound toneighboring support nano-particles are less likely to migrate on themicron-sized carrier particle surface and agglomerate into largercatalyst and/or PNA clumps. Since the larger agglomerations of catalystand/or PNA have less surface area and are less effective as catalystsand NO_(x) adsorbers, the inhibition of migration and agglomerationprovides a significant advantage for the NNm™ and NNiM particles. Incontrast, PGM particles deposited solely by wet-chemical precipitationonto alumina support demonstrate higher mobility and migration, formingagglomerations of PGM and leading to decreased catalytic efficacy overtime (that is, catalyst aging).

PNA Material (or Composition)

A PNA material or composition is a material that holds NO_(x) gasesduring low temperature engine operation and releases the gases when thetemperature rises to a threshold temperature. PNA material can be madeup of a single type of particle or multiple types of particles. PNAmaterial can also refer to a PNA washcoat composition or a PNA layer ona substrate.

The PNA material can comprise PGM on support particles; alkali oxide oralkaline earth oxide on support particles; alkali oxide or alkalineearth oxide and PGM on support particles; a combination of alkali oxideor alkaline earth oxide on support particles and different alkali oxidesor alkaline earth oxides each on different support particles in anyratio; a combination of alkali oxide or alkaline earth oxide on supportparticles and PGM on support particles in any ratio; a combination ofalkali oxide or alkaline earth oxide on support particles, differentalkali oxides or alkaline earth oxides each on different supportparticles, and PGM on support particles in any ratio; a combination ofalkali oxide or alkaline earth oxide and PGM on support particles andthe same or different alkali oxides or alkaline earth oxides each ondifferent support particles in any ratio; a combination of alkali oxideor alkaline earth oxide and PGM on support particles and PGM on supportparticles in any ratio; a combination of alkali oxide or alkaline earthoxide and PGM on support particles; the same or different alkali oxidesor alkaline earth oxides each on different support particles; and PGM onsupport particles in any ratio. In addition, various other combinationsof PGM on support particles; alkali oxides and alkaline earth oxides onsupport particles; and alkali oxides and alkaline earth oxides and PGMon support particles in any ratio can be employed. These PGM particlescan refer to any of the above mentioned catalytic particles.

The alkali oxides or alkaline earth oxides can include, for example,magnesium oxide, calcium oxide, manganese oxide, barium oxide, andstrontium oxide. The PGM can include, for example, palladium, ruthenium,or mixtures thereof. In addition, the PGM can include their oxides, suchas ruthenium oxide.

In some embodiments, the PNA material can comprise palladium on supportparticles; ruthenium or ruthenium oxide on support particles; manganeseoxide (preferably Mn₃O₄) on support particles; magnesium oxide onsupport particles; calcium oxide on support particles; a combination ofmanganese oxide on support particles and magnesium oxide on supportparticles in any ratio; a combination of manganese oxide on supportparticles and calcium oxide on support particles in any ratio; acombination of magnesium oxide on support particles and calcium oxide onsupport particles in any ratio; or a combination of manganese oxide onsupport particles, magnesium oxide on support particles, and calciumoxide on support particles in any ratio. Other embodiments include PNAmaterial comprising a combination of manganese oxide on supportparticles and PGM on support particles in any ratio; a combination ofmagnesium oxide on support particles and PGM on support particles in anyratio; a combination of calcium oxide on support particles and PGM onsupport particles in any ratio; a combination of manganese oxide onsupport particles, magnesium oxide on support particles, and PGM onsupport particles in any ratio; a combination of manganese oxide onsupport particles, calcium oxide on support particles, and PGM onsupport particles in any ratio; a combination of magnesium oxide onsupport particles, calcium oxide on support particles, and PGM onsupport particles in any ratio; or a combination of manganese oxide onsupport particles, magnesium oxide on support particles, calcium oxideon support particles, and PGM on support particles in any ratio.

Support particles can include, for example, bulk refractory oxides suchas alumina or cerium oxide. The cerium oxide particles may furthercomprise zirconium oxide. The cerium oxide particles may furthercomprise lanthanum and/or lanthanum oxide. In addition, the cerium oxideparticles may further comprise both zirconium oxide and lanthanum oxide.In some embodiments, the cerium oxide particles may further compriseyttrium oxide. Accordingly, the cerium oxide particles can be ceriumoxide, cerium-zirconium oxide, cerium-lanthanum oxide, cerium-yttriumoxide, cerium-zirconium-lanthanum oxide, cerium-zirconium-yttrium oxide,cerium-lanthanum-yttrium oxide, cerium-zirconium-lanthanum-yttrium oxideparticles, or a combination thereof. In some embodiments, the nano-sizedcerium oxide particles contain 40-90 wt % cerium oxide, 5-60 wt %zirconium oxide, 1-15 wt % lanthanum oxide, and/or 1-10 wt % yttriumoxide. In one embodiment, the cerium oxide particles contain 86 wt %cerium oxide, 10 wt % zirconium oxide, and 4 wt % lanthanum and/orlanthanum oxide. In another embodiment, the cerium oxide particlescontain 40 wt % cerium oxide, 50 wt % zirconium oxide, 5 wt % lanthanumoxide, and 5 wt % yttrium oxide.

The support particles can be micron-sized, nano-sized, or a mixturethereof. An example of micron-sized support particles includemicron-sized cerium oxide particles including, but not limited to, HSA5,HSA20, or a mixture thereof from Rhodia-Solvay.

In some embodiments, the support particles may include PGM, alkalioxides, and/or alkaline earth oxides. For example, the micron-sizedcerium oxide particles may include palladium, ruthenium, or a mixturethereof in addition to alkali oxide or alkaline earth oxide or mixturesthereof.

In some embodiments, different PNA materials may not be mixed on asupport material. For example, if a combination of manganese oxide oncerium oxide support and magnesium oxide on cerium oxide support isused, the manganese oxide is impregnated onto cerium oxide supportmaterial and set aside. Separately, magnesium oxide is then impregnatedonto fresh cerium oxide support material. The manganese oxide/ceriumoxide and magnesium oxide/cerium oxide are then combined in the desiredratio of the PNA material.

The PNA materials are adsorbers that hold NO_(x) compounds during lowtemperature engine operation. These gases are then released and reducedby the catalysts during high temperature engine operation. During lowtemperature engine operation, PNA particles physisorbs the NO_(x) vianon-covalent adsorption. Subsequently, during high temperature engineoperation, the NO_(x) sharply releases from the PNA particles. In thisway, the released NO_(x) can then be reduced to the benign gases N₂ andH₂O.

PGM, Alkali Oxide, and Alkaline Earth Oxide Nanoparticles andMicron-Particles

Alkali oxide, alkaline earth oxide, and PGM nanoparticles may beincluded in an oxidative washcoat layer, a reductive washcoat layer, aPNA layer, a zeolite layer, or any combination of the oxidative,reductive, PNA, and zeolite washcoat layers. As an alternativeembodiment, micron-sized alkali oxide, alkaline earth oxide, and PGMparticles may be included in any combination of the oxidative,reductive, PNA, and zeolite washcoat layers. In another alternativeembodiment, both nanoparticles and micron particles of alkali oxide,alkaline earth oxide, and PGM may be included in any combination of theoxidative, reductive, PNA, and zeolite washcoat layers.

Alkali oxides, alkaline earth oxides, and PGM particles are adsorbersthat hold NO_(x) compounds during low temperature engine operation. TheNO_(x) compounds are then released and reduced by catalysts during hightemperature engine operation. The temperature at which the NO_(x)compounds are released varies depending on the oxide, PGM, combinationof oxides, or combination of oxides and PGM, among other factors. Forexample, alkali oxides or alkaline earth oxides can be used to releaseNO_(x) compounds at temperatures lower than PGM particles. In addition,the alkali oxides or alkaline earth oxides can be magnesium oxide,calcium oxide, manganese oxide, barium oxide, and/or strontium oxide.Furthermore, the PGM can be palladium, ruthenium, or mixtures thereof.When used alone or in combination with other NO_(x) adsorbing materials,such as those described herein, the amount of PGM needed to store NO_(x)gases can be substantially reduced or even eliminated.

Alkali oxide, alkaline earth oxide, and PGM nanoparticles and micronparticles on support particles may be produced via wet chemistrytechniques or by the plasma-based methods described above. The PNAnanoparticles can include the composite nanoparticles described above.As such, the alkali oxide, alkaline earth oxide, and PGM nanoparticleson support particles can include PNA nano-on-nano particles, PNA NNmparticles, PNA NNiM particles, or PNA hybrid NNm/wet-chemistry particlesdescribed above.

In some embodiments, the alkali oxide, alkaline earth oxide, and PGMnanoparticles have an average diameter of approximately 20 nm or less,or approximately 15 nm or less, or approximately 10 nm or less, orapproximately 5 nm or less, or between approximately 1 nm andapproximately 20 nm, that is, approximately 10.5 nm±9.5 nm, or betweenapproximately 1 nm and approximately 15 nm, that is, approximately 8nm±7 nm, or between approximately 1 nm and approximately 10 nm, that is,approximately 5.5 nm±4.5 nm, or between approximately 1 nm andapproximately 5 nm, that is, approximately 3 nm±2 nm. In someembodiments, the alkali oxide, alkaline earth oxide, and PGMnanoparticles have a diameter of approximately 20 nm or less, orapproximately 15 nm or less, or approximately 10 nm or less, orapproximately 5 nm or less, or between approximately 1 nm andapproximately 10 nm, that is, approximately 5.5 nm±4.5 nm, or betweenapproximately 1 nm and approximately 5 nm, that is, approximately 3 nm±2nm.

In some embodiments, the alkali oxide, alkaline earth oxide, and PGMmicron particles may have an average diameter of approximately 10 μm orless, or approximately 8 μm or less, or approximately 5 μm or less, orapproximately 2 μm or less, or approximately 1.5 μm or less, orapproximately 1 μm or less, or approximately 0.5 μm or less. In someembodiments, the alkali oxide, alkaline earth oxide, and PGM micronparticles have an average diameter between approximately 6 μm andapproximately 10 μm, that is, approximately 8 μm±2 μm, or betweenapproximately 7 μm and approximately 9 μm, that is, approximately 8 μm±1μm. In some embodiments, the alkali oxide, alkaline earth oxide, and PGMmicron particles have an average diameter between approximately 0.5 μmand approximately 2 μm, that is, approximately 1.25 μm±0.75 μm, orbetween approximately 1.0 μm and approximately 1.5 μm, that is,approximately 1.25 μm±0.25 μm.

The alkali oxide, alkaline earth oxide, and PGM particles can be appliedto support particles by any of the processes described above withrespect to applying nanoparticles to support and/or carrier particlesincluding wet chemistry, incipient wetness, and plasma nano-on-nanomethods. These support particles can be nano-sized or micron-sized. Inaddition, these support particles can be, for example, refractory oxidesincluding cerium oxide. As discussed above, the cerium oxide particlesmay contain zirconium oxide, lanthanum, lanthanum oxide, yttrium oxide,or a combination thereof.

In one embodiment, the oxide and PGM nanoparticles can be impregnatedinto micron-sized cerium oxide supports. The procedure for impregnatingthese supports may be similar to the process described above withrespect to impregnating the composite nanoparticles into micron-sizedcerium oxide supports. One of ordinary skill in the art would understandthat the support particles can be impregnated one at a time orsimultaneously co-impregnated with the alkali and/or alkaline earthoxides and PGM. In some embodiments, the alkali oxide, alkaline earthoxide, and PGM nanoparticles on supports can be prepared by applying adispersion of alkali oxide, alkaline earth oxide, or PGM nanoparticlesto porous, micron-sized cerium oxide, as described with respect toincipient wetness techniques described above, including subsequentdrying and calcination. In some embodiments, the alkali oxide, alkalineearth oxide, and PGM nanoparticles on supports can be prepared using wetchemistry techniques described above, including subsequent drying andcalcination. The porous, micron-sized cerium oxide powders may containzirconium oxide, lanthanum, yttrium oxide, and/or lanthanum oxide. Insome embodiments, the cerium oxide is substantially free of zirconiumoxide. In other embodiments, the cerium oxide contains up to 50 mole %zirconium oxide (at exactly 50 mole %, the material is cerium-zirconiumoxide, CeZrO₄). One commercial cerium oxide powder suitable for use isHSA5, HSA20, or a mixture thereof. These nanoparticles may also beimpregnated into micron-sized aluminum oxide supports.

In one embodiment, palladium is used in an amount of from about 0.01% toabout 5% (by weight) of the amount of cerium oxide used in the PNAmaterial (i.e., composition). (As described above, in all embodiments,the cerium oxide can include zirconium oxide, lanthanum, lanthanumoxide, yttrium oxide, or a combination thereof). In one embodiment,palladium is used in an amount of from about 0.5% to about 3% (byweight) of the amount of cerium oxide used in the PNA material. In oneembodiment, palladium is used in an amount of from about 0.67% to about2.67% (by weight) of the amount of cerium oxide used in the PNAmaterial. In another embodiment, the amount of cerium oxide used in thePNA material is from about 50 g/L to about 400 g/L. In anotherembodiment, the amount of cerium oxide used in the PNA material is fromabout 100 g/L to about 350 g/L. In another embodiment, the amount ofcerium oxide used in the PNA material is from about 150 g/L to about 300g/L. In another embodiment, the amount of cerium oxide used in the PNAmaterial is greater than or equal to about 150 g/L. In anotherembodiment, Pd is used in an amount of from about 1.5% to about 2.5% (byweight) of the amount of cerium oxide used in the PNA material, and theamount of cerium oxide used is from about 100 g/L to about 200 g/L. Inanother embodiment, Pd is used in an amount of from about 0.5% to about1.5% (by weight) of the amount of cerium oxide used in the PNA material,and the amount of cerium oxide used is from about 250 g/L to about 350g/L. In another embodiment, Pd is used in an amount of from about 1% toabout 2% (by weight) of the amount of cerium oxide used in the PNAmaterial, and the amount of cerium oxide used is greater than or equalto about 150 g/L. In another embodiment, Pd is used in an amount ofabout 2% (by weight) of the amount of cerium oxide used in the PNAmaterial, and the amount of cerium oxide used is greater than or equalto about 150 g/L. In another embodiment, Pd is used in an amount ofabout 1% (by weight) of the amount of cerium oxide used in the PNAmaterial, and the amount of cerium oxide used is greater than or equalto about 300 g/L. In another embodiment, Pd is used in an amount ofabout 1 g/L to about 5 g/L. In another embodiment, Pd is used in anamount of about 2 g/L to about 4 g/L. In another embodiment, Pd is usedin an amount of about 3 g/L. In another embodiment, Pd is used in anamount of about 1 g/L to about 5 g/L, and the amount of cerium oxideused in the PNA material is from about 100 g/L to about 350 g/L. Inanother embodiment, Pd is used in an amount of about 2 g/L to about 4g/L, and the amount of cerium oxide used in the PNA material is fromabout 100 g/L to about 350 g/L. In another embodiment, Pd is used in anamount of about 3 g/L, and the amount of cerium oxide used in the PNAmaterial is from about 150 g/L to about 300 g/L. In another embodiment,Pd is used in an amount of about 1 g/L to about 5 g/L, and the amount ofcerium oxide used in the PNA material is from greater than or equal toabout 150 g/L. In another embodiment, Pd is used in an amount of about 2g/L to about 4 g/L, and the amount of cerium oxide used in the PNAmaterial is from greater than or equal to about 150 g/L. In anotherembodiment, Pd is used in an amount of about 3 g/L, and the amount ofcerium oxide used in the PNA material is from greater than or equal toabout 150 g/L. The PNA material can include Pd in larger (cooler) enginesystems (e.g., greater than 2.5 Liters).

In one embodiment, ruthenium is used in an amount of from about 0.01% toabout 15% (by weight) of the amount of cerium oxide used in the PNAmaterial (i.e., composition). (As described above, in all embodiments,the cerium oxide can include zirconium oxide, lanthanum, lanthanumoxide, yttrium oxide, or a combination thereof). In one embodiment,ruthenium is used in an amount of from about 0.5% to about 12% (byweight) of the amount of cerium oxide used in the PNA material. In oneembodiment, ruthenium is used in an amount of from about 1% to about 10%(by weight) of the amount of cerium oxide used in the PNA material. Inanother embodiment, the amount of cerium oxide used in the PNA materialis from about 50 g/L to about 400 g/L. In another embodiment, the amountof cerium oxide used in the PNA material is from about 100 g/L to about350 g/L. In another embodiment, the amount of cerium oxide used in thePNA material is from about 150 g/L to about 300 g/L. In anotherembodiment, the amount of cerium oxide used in the PNA material isgreater than or equal to about 150 g/L. In another embodiment, theamount of cerium oxide used in the PNA material is greater than or equalto about 300 g/L. In another embodiment, Ru is used in an amount of fromabout 3% to about 4.5% (by weight) of the amount of cerium oxide used inthe PNA material, and the amount of cerium oxide used is from about 100g/L to about 200 g/L. In another embodiment, Ru is used in an amount offrom about 1% to about 2.5% (by weight) of the amount of cerium oxideused in the PNA material, and the amount of cerium oxide used is fromabout 250 g/L to about 350 g/L. In another embodiment, Ru is used in anamount of from about 1.67% to about 4% (by weight) of the amount ofcerium oxide used in the PNA material, and the amount of cerium oxideused is greater than or equal to about 150 g/L. In another embodiment,Ru is used in an amount of from about 1.67% to about 4% (by weight) ofthe amount of cerium oxide used in the PNA material, and the amount ofcerium oxide used is greater than or equal to about 300 g/L. In anotherembodiment, Ru is used in an amount of about 3.33% to about 4% (byweight) of the amount of cerium oxide used in the PNA material, and theamount of cerium oxide used is greater than or equal to about 150 g/L.In another embodiment, Ru is used in an amount of about 1.67% to about2% (by weight) of the amount of cerium oxide used in the PNA material,and the amount of cerium oxide used is greater than or equal to about300 g/L. In another embodiment, Ru is used in an amount of about 1 g/Lto about 20 g/L. In another embodiment, Ru is used in an amount of about3 g/L to about 15 g/L. In another embodiment, Ru is used in an amount ofabout 4 g/L to about 8 g/L. In another embodiment, Ru is used in anamount of about 5 g/L to about 6 g/L. In another embodiment, Ru is usedin an amount of about 1 g/L to about 20 g/L, and the amount of ceriumoxide used in the PNA material is from about 100 g/L to about 350 g/L.In another embodiment, Ru is used in an amount of about 3 g/L to about15 g/L, and the amount of cerium oxide used in the PNA material is fromabout 100 g/L to about 350 g/L. In another embodiment, Ru is used in anamount of about 4 g/L to about 8 g/L, and the amount of cerium oxideused in the PNA material is from about 100 g/L to about 350 g/L. Inanother embodiment, Ru is used in an amount of about 5 g/L to about 6g/L, and the amount of cerium oxide used in the PNA material is fromabout 150 g/L to about 350 g/L. In another embodiment, Ru is used in anamount of about 1 g/L to about 20 g/L, and the amount of cerium oxideused in the PNA material is from greater than or equal to about 150 g/L.In another embodiment, Ru is used in an amount of about 3 g/L to about15 g/L, and the amount of cerium oxide used in the PNA material is fromgreater than or equal to about 150 g/L. In another embodiment, Ru isused in an amount of about 4 g/L to about 8 g/L, and the amount ofcerium oxide used in the PNA material is from greater than or equal toabout 150 g/L. In another embodiment, Ru is used in an amount of about 5g/L to about 6 g/L, and the amount of cerium oxide used in the PNAmaterial is from greater than or equal to about 150 g/L. In anotherembodiment, Ru is used in an amount of about 1 g/L to about 20 g/L, andthe amount of cerium oxide used in the PNA material is from greater thanor equal to about 300 g/L. In another embodiment, Ru is used in anamount of about 3 g/L to about 15 g/L, and the amount of cerium oxideused in the PNA material is from greater than or equal to about 300 g/L.In another embodiment, Ru is used in an amount of about 4 g/L to about 8g/L, and the amount of cerium oxide used in the PNA material is fromgreater than or equal to about 300 g/L. In another embodiment, Ru isused in an amount of about 5 g/L to about 6 g/L, and the amount ofcerium oxide used in the PNA material is from greater than or equal toabout 300 g/L. The PNA material can include Ru in small (hotter) enginesystems (e.g., less than 2 Liters).

In one embodiment, MgO is used in an amount of from about 1% to about20% (by weight) of the amount of the cerium oxide used in the PNAmaterial (i.e., composition). In one embodiment, MgO is used in anamount of from about 1% to about 15% (by weight) of the amount of thecerium oxide used in the PNA material. In one embodiment, MgO is used inan amount of from about 1% to about 10% (by weight) of the amount of thecerium oxide used in the PNA material. In another embodiment, the amountof cerium oxide used in the PNA material is from about 50 g/L to about450 g/L. In another embodiment, the amount of cerium oxide used in thePNA material is from about 100 g/L to about 400 g/L. In anotherembodiment, the amount of cerium oxide used in the PNA material is fromabout 150 g/L to about 350 g/L. In another embodiment, MgO is used in anamount of from about 2% to about 8% (by weight) of the amount of thecerium oxide used in the PNA material, and the amount of cerium oxideused is from about 150 g/L to about 350 g/L. In another embodiment, MgOis used in an amount of from about 2% to about 4% (by weight) of theamount of the cerium oxide used in the PNA material, and the amount ofcerium oxide used is from about 250 g/L to about 350 g/L. In anotherembodiment, MgO is used in an amount of from about 6% to about 8% (byweight) of the amount of the cerium oxide used in the PNA material, andthe amount of cerium oxide used is from about 150 g/L to about 250 g/L.In another embodiment, MgO is used in an amount of about 3% (by weight)of the amount of the cerium oxide used in the PNA material, and theamount of cerium oxide used in the PNA material is about 350 g/L. Inanother embodiment, MgO is used in an amount of about 7% (by weight) ofthe amount of the cerium oxide used in the PNA material, and the amountof cerium oxide used is about 150 g/L. In another embodiment, MgO isused in an amount of about 10.5 g/L, and the amount of cerium oxide usedin the PNA material is from about 150 g/L to about 350 g/L.

In one embodiment, Mn₃O₄ is used in an amount of from about 1% to about30% (by weight) of the amount of the cerium oxide used in the PNAmaterial (i.e., composition). In one embodiment, Mn₃O₄ is used in anamount of from about 1% to about 25% (by weight) of the amount of thecerium oxide used in the PNA material. In one embodiment, Mn₃O₄ is usedin an amount of from about 1% to about 20% (by weight) of the amount ofthe cerium oxide used in the PNA material. In another embodiment, theamount of cerium oxide used in the PNA material is from about 50 g/L toabout 450 g/L. In another embodiment, the amount of cerium oxide used inthe PNA material is from about 100 g/L to about 400 g/L. In anotherembodiment, the amount of cerium oxide used in the PNA material is fromabout 150 g/L to about 350 g/L. In another embodiment, Mn₃O₄ is used inan amount of from about 5% to about 20% (by weight) of the amount of thecerium oxide used in the PNA material, and the amount of cerium oxideused is from about 150 g/L to about 350 g/L. In another embodiment,Mn₃O₄ is used in an amount of from about 5% to about 10% (by weight) ofthe amount of the cerium oxide used in the PNA material, and the amountof cerium oxide used is from about 250 g/L to about 350 g/L. In anotherembodiment, Mn₃O₄ is used in an amount of from about 15% to about 20%(by weight) of the amount of the cerium oxide used in the PNA material,and the amount of cerium oxide used is from about 150 g/L to about 250g/L. In another embodiment, Mn₃O₄ is used in an amount of about 8% (byweight) of the amount of the cerium oxide used in the PNA material, andthe amount of cerium oxide used is about 350 g/L. In another embodiment,Mn₃O₄ is used in an amount of about 18.67% (by weight) of the amount ofthe cerium oxide used in the PNA material, and the amount of ceriumoxide used is about 150 g/L. In another embodiment, Mn₃O₄ is used in anamount of about 28 g/L, and the amount of cerium oxide used in the PNAmaterial is from about 150 g/L to about 350 g/L.

In one embodiment, calcium oxide is used in an amount of from about 1%to about 20% (by weight) of the amount of the cerium oxide used in thePNA material (i.e., composition). In one embodiment, calcium oxide isused in an amount of from about 1% to about 15% (by weight) of theamount of the cerium oxide used in the PNA material. In one embodiment,calcium oxide is used in an amount of from about 1% to about 10% (byweight) of the amount of the cerium oxide used in the PNA material. Inanother embodiment, the amount of cerium oxide used in the PNA materialis from about 50 g/L to about 450 g/L. In another embodiment, the amountof cerium oxide used in the PNA material is from about 100 g/L to about400 g/L. In another embodiment, the amount of cerium oxide used in thePNA material is from about 150 g/L to about 350 g/L. In anotherembodiment, calcium oxide is used in an amount of from about 2% to about8% (by weight) of the amount of the cerium oxide used in the PNAmaterial, and the amount of cerium oxide used is from about 150 g/L toabout 350 g/L. In another embodiment, calcium oxide is used in an amountof from about 2% to about 4% (by weight) of the amount of the ceriumoxide used in the PNA material, and the amount of cerium oxide used isfrom about 250 g/L to about 350 g/L. In another embodiment, calciumoxide is used in an amount of from about 6% to about 8% (by weight) ofthe amount of the cerium oxide used in the PNA material, and the amountof cerium oxide used is from about 150 g/L to about 250 g/L. In anotherembodiment, calcium oxide is used in an amount of about 3% (by weight)of the amount of the cerium oxide used in the PNA material, and theamount of cerium oxide used is about 350 g/L. In another embodiment,calcium oxide is used in an amount of about 7% (by weight) of the amountof the cerium oxide used in the PNA material, and the amount of ceriumoxide used is about 150 g/L. In another embodiment, calcium oxide isused in an amount of about 10.5 g/L, and the amount of cerium oxide usedin the PNA material is from about 150 g/L to about 350 g/L.

In one embodiment, MgO is used in an amount of about 10.5 g/L, Mn₃O₄ isused in an amount of about 28 g/L, calcium oxide is used in an amount ofabout 10.5 g/L, and the amount of cerium oxide used in the PNA material(i.e., composition) is from about 150 g/L to about 350 g/L.

The PNA material can be used to store NO_(x) emissions from ambienttemperatures to a variety of operating temperatures. For example, thePNA material can store NO_(x) emissions from ambient to about 100° C.,105° C., 110° C., 115° C., 120° C., 125° C., 130° C., 135° C., 140° C.,145° C., 150° C., 155° C., 160° C., 165° C., 170° C., 175° C., 180° C.,185° C., 190° C., 195° C., 200° C., 205° C., 210° C., 215° C., 220° C.,225° C., 230° C., 235° C., 240° C., 245° C., 250° C., 255° C., 260° C.,265° C., 270° C., 275° C., 280° C., 285° C., 290° C., 295° C., 300° C.,305° C., 310° C., 315° C., 320° C., 325° C., 330° C., 335° C., 340° C.,345° C., 350° C., 355° C., 375° C., or 400° C.

In one embodiment, palladium based PNA material can be used for storingNO_(x) emissions from ambient temperature to greater than or equal toabout 200° C. In another embodiment, Pd based PNA material can be usedfor storing NO_(x) emissions from ambient temperature to greater than orequal to about 190° C. In another embodiment, Pd based PNA material canbe used for storing NO_(x) emissions from ambient temperature to greaterthan or equal to about 180° C. In another embodiment, Pd based PNAmaterial can be used for storing NO_(x) emissions from ambienttemperature to greater than or equal to about 170° C. In anotherembodiment, Pd based PNA material can be used for storing NO_(x)emissions from ambient temperature to greater than or equal to about160° C. In another embodiment, Pd based PNA material can be used forstoring NO_(x) emissions from ambient temperature to greater than orequal to about 150° C. In another embodiment, Pd based PNA material canbe used for storing NO_(x) emissions from ambient temperature to greaterthan or equal to about 140° C. Once the temperature surpasses the upperstorage temperature, the PNA material can “cross over” (i.e., can stopadsorbing NO_(x) emissions and can start releasing the NO_(x)emissions). The cross over range for Pd based PNA material can be fromabout 130° C. to about 180° C., from about 140° C. to about 170° C.,from about 145° C. to about 165° C., or from about 150° C. to about 160°C.

The NO_(x) desorption temperature range depends on a variety of factorsincluding the amount of PGM in the PNA material. In one embodiment, thedesorption temperature range can be greater than or equal to the crossover temperature. At a certain temperature, the PNA material may nolonger be storing any NO_(x) emissions. At this point, the PNA materialcan be said to have fully released all NO_(x) emissions. In oneembodiment, the full release temperature of the Pd based PNA material isgreater than about 150° C. In one embodiment, the full releasetemperature of the Pd based PNA material is greater than about 200° C.In another embodiment, the full release temperature of the Pd based PNAmaterial is between about 200° C. and about 240° C. In anotherembodiment, the full release temperature of the Pd based PNA material isabout 240° C. In another embodiment, the full release temperature of thePd based PNA material is greater than about 240° C. In anotherembodiment, the Pd based PNA material no longer has any NO_(x) emissionsstored at temperatures greater than or equal to about 200° C. In anotherembodiment, the Pd based PNA material no longer has any NO_(x) emissionsstored at temperatures greater than or equal to about 240° C. In anotherembodiment, the Pd based PNA material no longer has any NO_(x) emissionsstored at temperatures from about 200° C. to about 300° C. In anotherembodiment, the Pd based PNA material no longer has any NO_(x) emissionsstored at about greater than or equal to 300° C.

In one embodiment, ruthenium based PNA material can be used for storingNO_(x) emissions from ambient temperature to greater than or equal toabout 300° C. In another embodiment, Ru based PNA material can be usedfor storing NO_(x) emissions from ambient temperature to greater than orequal to about 275° C. In another embodiment, Ru based PNA material canbe used for storing NO_(x) emissions from ambient temperature to greaterthan or equal to about 250° C. In another embodiment, Ru based PNAmaterial can be used for storing NO_(x) emissions from ambienttemperature to greater than or equal to about 225° C. In anotherembodiment, Ru based PNA material can be used for storing NO_(x)emissions from ambient temperature to greater than or equal to about200° C. In another embodiment, Ru based PNA material can be used forstoring NO_(x) emissions from ambient temperature to greater than orequal to about 190° C. Once the temperature surpasses the upper storagetemperature, the PNA material can “cross over” (i.e., can stop adsorbingNO_(x) emissions and can start releasing the NO_(x) emissions). Thecross over range for Ru based PNA material can be from about 170° C. toabout 220° C., from about 180° C. to about 210° C., from about 185° C.to about 205° C., or from about 190° C. to about 200° C.

The NO_(x) desorption temperature depends on a variety of factorsincluding the amount of PGM and/or oxide in the PNA material. In oneembodiment, the desorption temperature range can be greater than orequal to the cross over temperature. At a certain temperature, the PNAmaterial may no longer be storing any NO_(x) emissions. At this point,the PNA material can be said to have fully released all NO_(x)emissions. In one embodiment, the full release temperature of the Rubased PNA material is greater than about 200° C. In one embodiment, thefull release temperature of the Ru based PNA material is greater thanabout 250° C. In one embodiment, the full release temperature of the Rubased PNA material is greater than or equal to about 300° C. In oneembodiment, the full release temperature of the Ru based PNA material isgreater than or equal to about 340° C. In another embodiment, the fullrelease temperature of the Ru based PNA material is between about 300°C. and about 350° C. In another embodiment, the full release temperatureof the Ru based PNA material is about 340° C. In another embodiment, theRu based PNA material no longer has any NO_(x) emissions stored attemperatures greater than or equal to about 200° C. In anotherembodiment, the Ru based PNA material no longer has any NO_(x) emissionsstored at temperatures greater than or equal to about 250° C. In anotherembodiment, the Ru based PNA material no longer has any NO_(x) emissionsstored at temperatures greater than or equal to about 300° C. In anotherembodiment, the Ru based PNA material no longer has any NO_(x) emissionsstored at temperatures greater than or equal to about 340° C. In anotherembodiment, the Ru based PNA material no longer has any NO_(x) emissionsstored at temperatures from about 300° C. to about 400° C. In anotherembodiment, the Ru based PNA material no longer has any NO_(x) emissionsstored at temperatures greater than or equal to about 400° C.

In one embodiment, manganese oxide based PNA material can be used forstoring NO_(x) emissions from ambient temperature to about 150° C. Inanother embodiment, manganese oxide based PNA material can be used forstoring NO_(x) emissions from ambient temperature to about 125° C. Inanother embodiment, manganese oxide based PNA material can be used forstoring NO_(x) emissions from ambient temperature to about 110° C. Inanother embodiment, manganese oxide based PNA material can be used forstoring NO_(x) emissions from ambient temperature to about 100° C. Inanother embodiment, manganese oxide based PNA material can be used forstoring NO_(x) emissions from ambient temperature to less than about100° C. Once the temperature surpasses the upper storage temperature,the PNA material can “cross over” (i.e., can stop adsorbing NO_(x)emissions and can start releasing the NO_(x) emissions).

In one embodiment, the manganese oxide based PNA material no longer hasany NO_(x) emissions stored at temperatures from about 200° C. to about250° C. In another embodiment, the manganese oxide based PNA material nolonger has any NO_(x) emissions stored at temperatures from about 210°C. to about 240° C. In another embodiment, the manganese based PNAmaterial no longer has any NO_(x) emissions stored at temperatures fromabout 215° C. to about 225° C. In another embodiment, the manganesebased PNA material no longer has any NO_(x) emissions stored at about220° C.

In one embodiment, magnesium oxide based PNA material can be used forstoring NO_(x) emissions from ambient temperature to about 200° C. Inanother embodiment, magnesium oxide based PNA material can be used forstoring NO_(x) emissions from ambient temperature to about 175° C. Inanother embodiment, magnesium oxide based PNA material can be used forstoring NO_(x) emissions from ambient temperature to about 150° C. Inanother embodiment, magnesium oxide based PNA material can be used forstoring NO_(x) emissions from ambient temperature to less than about150° C. Once the temperature surpasses the upper storage temperature,the PNA material can “cross over” (i.e., can stop adsorbing NO_(x)emissions and can start releasing the NO_(x) emissions).

In one embodiment, the magnesium oxide based PNA material no longer hasany NO_(x) emissions stored at temperatures from about 210° C. to about260° C. In another embodiment, the magnesium oxide based PNA material nolonger has any NO_(x) emissions stored at temperatures from about 220°C. to about 250° C. In another embodiment, the magnesium based PNAmaterial no longer has any NO_(x) emissions stored at temperatures fromabout 235° C. to about 245° C. In another embodiment, the magnesiumbased PNA material no longer has any NO_(x) emissions stored at about240° C.

In one embodiment, calcium oxide based PNA material can be used forstoring NO_(x) emissions from ambient temperature to about 250° C. Inanother embodiment, calcium oxide based PNA material can be used forstoring NO_(x) emissions from ambient temperature to about 225° C. Inanother embodiment, calcium oxide based PNA material can be used forstoring NO_(x) emissions from ambient temperature to about 200° C. Inanother embodiment, calcium oxide based PNA material can be used forstoring NO_(x) emissions from ambient temperature to less than about200° C. In another embodiment, calcium oxide based PNA material can beused for storing NO_(x) emissions from ambient temperature to about 180°C. In another embodiment, calcium oxide based PNA material can be usedfor storing NO_(x) emissions from ambient temperature to less than about180° C. Once the temperature surpasses the upper storage temperature,the PNA material can “cross over” (i.e., can stop adsorbing NO_(x)emissions and can start releasing the NO_(x) emissions).

In one embodiment, the calcium oxide based PNA material no longer hasany NO_(x) emissions stored at temperatures from about 290° C. to about340° C. In another embodiment, the calcium oxide based PNA material nolonger has any NO_(x) emissions stored at temperatures from about 300°C. to about 330° C. In another embodiment, the calcium based PNAmaterial no longer has any NO_(x) emissions stored at temperatures fromabout 305° C. to about 315° C. In another embodiment, the calcium basedPNA material no longer has any NO_(x) emissions stored at about 310° C.

In some embodiments, the support particles are impregnated with alkalioxide, alkaline earth oxide, and PGM using wet chemistry techniques. Insome embodiments, the PNA material may be prepared by incipient wetnesstechniques. In some embodiments, the PNA material is prepared by plasmabased methods. In some embodiments, the PNA material includes NNmparticles, NNiM particles, and/or hybrid NNm/wet-chemistry particles. Inanother embodiment, alkali oxide, alkaline earth oxide, and PGM nano ormicron particles can be used simply by adding them to the washcoat whendesired, in the amount desired, along with the other solid ingredients.

PNA Material Compositions

The PNA material can comprise PGM on support particles, alkali oxide oralkaline earth oxide on support particles; alkali oxide or alkalineearth oxide and PGM on support particles; a combination of alkali oxideor alkaline earth oxide on support particles and different alkali oxidesor alkaline earth oxides each on different support particles in anyratio; a combination of alkali oxide or alkaline earth oxide on supportparticles and PGM on support particles in any ratio; a combination ofalkali oxide or alkaline earth oxide on support particles, differentalkali oxides or alkaline earth oxides each on different supportparticles, and PGM on support particles in any ratio; a combination ofalkali oxide or alkaline earth oxide and PGM on support particles andthe same or different alkali oxides or alkaline earth oxides each ondifferent support particles in any ratio; a combination of alkali oxideor alkaline earth oxide and PGM on support particles and PGM on supportparticles in any ratio; a combination of alkali oxide or alkaline earthoxide and PGM on support particles; the same or different alkali oxidesor alkaline earth oxides each on different support particles; and PGM onsupport particles in any ratio. In addition, various other combinationsof alkali oxides and alkaline earth oxides on support particles; PGM onsupport particles; and alkali oxides and alkaline earth oxides and PGMon support particles in any ratio can be employed, as discussed above.The PGM can include, for example, palladium, ruthenium, or mixturesthereof. In addition, the PGM can include their oxides, such asruthenium oxide.

In some embodiments, the PNA material can comprise palladium on supportparticles; ruthenium on support particles; manganese oxide (preferablyMn₃O₄) on support particles; magnesium oxide on support particles;calcium oxide on support particles; a combination of manganese oxide onsupport particles and magnesium oxide on support particles in any ratio;a combination of manganese oxide on support particles and calcium oxideon support particles in any ratio; a combination of magnesium oxide onsupport particles and calcium oxide on support particles in any ratio;or a combination of manganese oxide on support particles, magnesiumoxide on support particles, and calcium oxide on support particles inany ratio. Other embodiments include PNA material comprising acombination of manganese oxide on support particles and PGM on supportparticles in any ratio; a combination of magnesium oxide on supportparticles and PGM on support particles in any ratio; a combination ofcalcium oxide on support particles and PGM on support particles in anyratio; a combination of manganese oxide on support particles, magnesiumoxide on support particles, and PGM on support particles in any ratio; acombination of manganese oxide on support particles, calcium oxide onsupport particles, and PGM on support particles in any ratio; acombination of magnesium oxide on support particles, calcium oxide onsupport particles, and PGM on support particles in any ratio; or acombination of manganese oxide on support particles, magnesium oxide onsupport particles, calcium oxide on support particles, and PGM onsupport particles in any ratio, which are discussed above.

In some embodiments, different PNA materials may not be mixed on asupport material. For example, if a combination of manganese oxide oncerium oxide support and magnesium oxide on cerium oxide support isused, the manganese oxide is impregnated onto cerium oxide supportmaterial and set aside. Separately, magnesium oxide is then impregnatedonto fresh cerium oxide support material. The manganese oxide/ceriumoxide and magnesium oxide/cerium oxide are then combined in the desiredratio of the PNA material.

In one embodiment, palladium is used in an amount of from about 0.01% toabout 5% (by weight) of the amount of cerium oxide used in the PNAcomposition. (As described above, in all embodiments, the cerium oxidecan include zirconium oxide, lanthanum, lanthanum oxide, yttrium oxide,or a combination thereof). In one embodiment, palladium is used in anamount of from about 0.5% to about 3% (by weight) of the amount ofcerium oxide used in the PNA composition. In one embodiment, palladiumis used in an amount of from about 0.67% to about 2.67% (by weight) ofthe amount of cerium oxide used in the PNA composition. In anotherembodiment, the amount of cerium oxide used in the PNA composition isfrom about 50 g/L to about 400 g/L. In another embodiment, the amount ofcerium oxide used in the PNA composition is from about 100 g/L to about350 g/L. In another embodiment, the amount of cerium oxide used in thePNA composition is from about 150 g/L to about 300 g/L. In anotherembodiment, the amount of cerium oxide used in the PNA composition isgreater than or equal to about 150 g/L. In another embodiment, Pd isused in an amount of from about 1.5% to about 2.5% (by weight) of theamount of cerium oxide used in the PNA composition, and the amount ofcerium oxide used is from about 100 g/L to about 200 g/L. In anotherembodiment, Pd is used in an amount of from about 0.5% to about 1.5% (byweight) of the amount of cerium oxide used in the PNA composition, andthe amount of cerium oxide used is from about 250 g/L to about 350 g/L.In another embodiment, Pd is used in an amount of from about 1% to about2% (by weight) of the amount of cerium oxide used in the PNAcomposition, and the amount of cerium oxide used is greater than orequal to about 150 g/L. In another embodiment, Pd is used in an amountof about 2% (by weight) of the amount of cerium oxide used in the PNAcomposition, and the amount of cerium oxide used is greater than orequal to about 150 g/L. In another embodiment, Pd is used in an amountof about 1% (by weight) of the amount of cerium oxide used in the PNAcomposition, and the amount of cerium oxide used is greater than orequal to about 300 g/L. In another embodiment, Pd is used in an amountof about 1 g/L to about 5 g/L. In another embodiment, Pd is used in anamount of about 2 g/L to about 4 g/L. In another embodiment, Pd is usedin an amount of about 3 g/L. In another embodiment, Pd is used in anamount of about 1 g/L to about 5 g/L, and the amount of cerium oxideused in the PNA composition is from about 100 g/L to about 350 g/L. Inanother embodiment, Pd is used in an amount of about 2 g/L to about 4g/L, and the amount of cerium oxide used in the PNA composition is fromabout 100 g/L to about 350 g/L. In another embodiment, Pd is used in anamount of about 3 g/L, and the amount of cerium oxide used in the PNAcomposition is from about 150 g/L to about 300 g/L. In anotherembodiment, Pd is used in an amount of about 1 g/L to about 5 g/L, andthe amount of cerium oxide used in the PNA composition is from greaterthan or equal to about 150 g/L. In another embodiment, Pd is used in anamount of about 2 g/L to about 4 g/L, and the amount of cerium oxideused in the PNA composition is from greater than or equal to about 150g/L. In another embodiment, Pd is used in an amount of about 3 g/L, andthe amount of cerium oxide used in the PNA composition is from greaterthan or equal to about 150 g/L. The PNA composition can include Pd inlarger (cooler) engine systems (e.g., greater than 2.5 Liters).

In one embodiment, ruthenium is used in an amount of from about 0.01% toabout 15% (by weight) of the amount of cerium oxide used in the PNAcomposition. (As described above, in all embodiments, the cerium oxidecan include zirconium oxide, lanthanum, lanthanum oxide, yttrium oxide,or a combination thereof). In one embodiment, ruthenium is used in anamount of from about 0.5% to about 12% (by weight) of the amount ofcerium oxide used in the PNA composition. In one embodiment, rutheniumis used in an amount of from about 1% to about 10% (by weight) of theamount of cerium oxide used in the PNA composition. In anotherembodiment, the amount of cerium oxide used in the PNA composition isfrom about 50 g/L to about 400 g/L. In another embodiment, the amount ofcerium oxide used in the PNA composition is from about 100 g/L to about350 g/L. In another embodiment, the amount of cerium oxide used in thePNA composition is from about 150 g/L to about 300 g/L. In anotherembodiment, the amount of cerium oxide used in the PNA composition isgreater than or equal to about 150 g/L. In another embodiment, theamount of cerium oxide used in the PNA composition is greater than orequal to about 300 g/L. In another embodiment, Ru is used in an amountof from about 3% to about 4.5% (by weight) of the amount of cerium oxideused in the PNA composition, and the amount of cerium oxide used is fromabout 100 g/L to about 200 g/L. In another embodiment, Ru is used in anamount of from about 1% to about 2.5% (by weight) of the amount ofcerium oxide used in the PNA composition, and the amount of cerium oxideused is from about 250 g/L to about 350 g/L. In another embodiment, Ruis used in an amount of from about 1.67% to about 4% (by weight) of theamount of cerium oxide used in the PNA composition, and the amount ofcerium oxide used is greater than or equal to about 150 g/L. In anotherembodiment, Ru is used in an amount of from about 1.67% to about 4% (byweight) of the amount of cerium oxide used in the PNA composition, andthe amount of cerium oxide used is greater than or equal to about 300g/L. In another embodiment, Ru is used in an amount of about 3.33% toabout 4% (by weight) of the amount of cerium oxide used in the PNAcomposition, and the amount of cerium oxide used is greater than orequal to about 150 g/L. In another embodiment, Ru is used in an amountof about 1.67% to about 2% (by weight) of the amount of cerium oxideused in the PNA composition, and the amount of cerium oxide used isgreater than or equal to about 300 g/L. In another embodiment, Ru isused in an amount of about 1 g/L to about 20 g/L. In another embodiment,Ru is used in an amount of about 3 g/L to about 15 g/L. In anotherembodiment, Ru is used in an amount of about 4 g/L to about 8 g/L. Inanother embodiment, Ru is used in an amount of about 5 g/L to about 6g/L. In another embodiment, Ru is used in an amount of about 1 g/L toabout 20 g/L, and the amount of cerium oxide used in the PNA compositionis from about 100 g/L to about 350 g/L. In another embodiment, Ru isused in an amount of about 3 g/L to about 15 g/L, and the amount ofcerium oxide used in the PNA composition is from about 100 g/L to about350 g/L. In another embodiment, Ru is used in an amount of about 4 g/Lto about 8 g/L, and the amount of cerium oxide used in the PNAcomposition is from about 100 g/L to about 350 g/L. In anotherembodiment, Ru is used in an amount of about 5 g/L to about 6 g/L, andthe amount of cerium oxide used in the PNA composition is from about 150g/L to about 350 g/L. In another embodiment, Ru is used in an amount ofabout 1 g/L to about 20 g/L, and the amount of cerium oxide used in thePNA composition is from greater than or equal to about 150 g/L. Inanother embodiment, Ru is used in an amount of about 3 g/L to about 15g/L, and the amount of cerium oxide used in the PNA composition is fromgreater than or equal to about 150 g/L. In another embodiment, Ru isused in an amount of about 4 g/L to about 8 g/L, and the amount ofcerium oxide used in the PNA composition is from greater than or equalto about 150 g/L. In another embodiment, Ru is used in an amount ofabout 5 g/L to about 6 g/L, and the amount of cerium oxide used in thePNA composition is from greater than or equal to about 150 g/L. Inanother embodiment, Ru is used in an amount of about 1 g/L to about 20g/L, and the amount of cerium oxide used in the PNA composition is fromgreater than or equal to about 300 g/L. In another embodiment, Ru isused in an amount of about 3 g/L to about 15 g/L, and the amount ofcerium oxide used in the PNA composition is from greater than or equalto about 300 g/L. In another embodiment, Ru is used in an amount ofabout 4 g/L to about 8 g/L, and the amount of cerium oxide used in thePNA composition is from greater than or equal to about 300 g/L. Inanother embodiment, Ru is used in an amount of about 5 g/L to about 6g/L, and the amount of cerium oxide used in the PNA composition is fromgreater than or equal to about 300 g/L. The PNA composition can includeRu in small (hotter) engine systems (e.g., less than 2 Liters).

In one embodiment, MgO is used in an amount of from about 1% to about20% (by weight) of the amount of the cerium oxide used in the PNAcomposition. In one embodiment, MgO is used in an amount of from about1% to about 15% (by weight) of the amount of the cerium oxide used inthe PNA composition. In one embodiment, MgO is used in an amount of fromabout 1% to about 10% (by weight) of the amount of the cerium oxide usedin the PNA composition. In another embodiment, the amount of ceriumoxide used in the PNA composition is from about 50 g/L to about 450 g/L.In another embodiment, the amount of cerium oxide used in the PNAcomposition is from about 100 g/L to about 400 g/L. In anotherembodiment, the amount of cerium oxide used in the PNA composition isfrom about 150 g/L to about 350 g/L. In another embodiment, MgO is usedin an amount of from about 2% to about 8% (by weight) of the amount ofthe cerium oxide used in the PNA composition, and the amount of ceriumoxide used is from about 150 g/L to about 350 g/L. In anotherembodiment, MgO is used in an amount of from about 2% to about 4% (byweight) of the amount of the cerium oxide used in the PNA composition,and the amount of cerium oxide used is from about 250 g/L to about 350g/L. In another embodiment, MgO is used in an amount of from about 6% toabout 8% (by weight) of the amount of the cerium oxide used in the PNAcomposition, and the amount of cerium oxide used is from about 150 g/Lto about 250 g/L. In another embodiment, MgO is used in an amount ofabout 3% (by weight) of the amount of the cerium oxide used in the PNAcomposition, and the amount of cerium oxide used is about 350 g/L. Inanother embodiment, MgO is used in an amount of about 7% (by weight) ofthe amount of the cerium oxide used in the PNA composition, and theamount of cerium oxide used is about 150 g/L. In another embodiment, MgOis used in an amount of about 10.5 g/L, and the amount of cerium oxideused in the PNA composition is from about 150 g/L to about 350 g/L.

In one embodiment, Mn₃O₄ is used in an amount of from about 1% to about30% (by weight) of the amount of the cerium oxide used in the PNAcomposition. In one embodiment, Mn₃O₄ is used in an amount of from about1% to about 25% (by weight) of the amount of the cerium oxide used inthe PNA composition. In one embodiment, Mn₃O₄ is used in an amount offrom about 1% to about 20% (by weight) of the amount of the cerium oxideused in the PNA composition. In another embodiment, the amount of ceriumoxide used in the PNA composition is from about 50 g/L to about 450 g/L.In another embodiment, the amount of cerium oxide used in the PNAcomposition is from about 100 g/L to about 400 g/L. In anotherembodiment, the amount of cerium oxide used in the PNA composition isfrom about 150 g/L to about 350 g/L. In another embodiment, Mn₃O₄ isused in an amount of from about 5% to about 20% (by weight) of theamount of the cerium oxide used in the PNA composition, and the amountof cerium oxide used is from about 150 g/L to about 350 g/L. In anotherembodiment, Mn₃O₄ is used in an amount of from about 5% to about 10% (byweight) of the amount of the cerium oxide used in the PNA composition,and the amount of cerium oxide used is from about 250 g/L to about 350g/L. In another embodiment, Mn₃O₄ is used in an amount of from about 15%to about 20% (by weight) of the amount of the cerium oxide used in thePNA composition, and the amount of cerium oxide used is from about 150g/L to about 250 g/L. In another embodiment, Mn₃O₄ is used in an amountof about 8% (by weight) of the amount of the cerium oxide used in thePNA composition, and the amount of cerium oxide used is about 350 g/L.In another embodiment, Mn₃O₄ is used in an amount of about 18.67% (byweight) of the amount of the cerium oxide used in the PNA composition,and the amount of cerium oxide used is about 150 g/L. In anotherembodiment, Mn₃O₄ is used in an amount of about 28 g/L, and the amountof cerium oxide used in the PNA composition is from about 150 g/L toabout 350 g/L.

In one embodiment, calcium oxide is used in an amount of from about 1%to about 20% (by weight) of the amount of the cerium oxide used in thePNA composition. In one embodiment, calcium oxide is used in an amountof from about 1% to about 15% (by weight) of the amount of the ceriumoxide used in the PNA composition. In one embodiment, calcium oxide isused in an amount of from about 1% to about 10% (by weight) of theamount of the cerium oxide used in the PNA composition. In anotherembodiment, the amount of cerium oxide used in the PNA composition isfrom about 50 g/L to about 450 g/L. In another embodiment, the amount ofcerium oxide used in the PNA composition is from about 100 g/L to about400 g/L. In another embodiment, the amount of cerium oxide used in thePNA composition is from about 150 g/L to about 350 g/L. In anotherembodiment, calcium oxide is used in an amount of from about 2% to about8% (by weight) of the amount of the cerium oxide used in the PNAcomposition, and the amount of cerium oxide used is from about 150 g/Lto about 350 g/L. In another embodiment, calcium oxide is used in anamount of from about 2% to about 4% (by weight) of the amount of thecerium oxide used in the PNA composition, and the amount of cerium oxideused in the PNA composition is from about 250 g/L to about 350 g/L. Inanother embodiment, calcium oxide is used in an amount of from about 6%to about 8% (by weight) of the amount of the cerium oxide used in thePNA composition, and the amount of cerium oxide used is from about 150g/L to about 250 g/L. In another embodiment, calcium oxide is used in anamount of about 3% (by weight) of the amount of the cerium oxide used inthe PNA composition, and the amount of cerium oxide used is about 350g/L. In another embodiment, calcium oxide is used in an amount of about7% (by weight) of the amount of the cerium oxide used in the PNAcomposition, and the amount of cerium oxide used is about 150 g/L. Inanother embodiment, calcium oxide is used in an amount of about 10.5g/L, and the amount of cerium oxide used in the PNA composition is fromabout 150 g/L to about 350 g/L.

In one embodiment, MgO is used in an amount of about 10.5 g/L, Mn₃O₄ isused in an amount of about 28 g/L, calcium oxide is used in an amount ofabout 10.5 g/L, and the amount of cerium oxide used in the PNAcomposition is from about 150 g/L to about 350 g/L.

The amount of cerium oxide can correspond to the total amount of ceriumoxide used to form the alkali oxide or alkaline earth oxide/ceriumoxide; PGM/cerium oxide (including if NNm or NNiM particles areemployed); the alkali oxide or alkaline earth oxide/cerium oxide andPGM/cerium oxide; the alkali oxide or alkaline earth oxide/cerium oxideand other alkali oxide(s) or alkaline earth oxide(s)/cerium oxide; orthe alkali oxide or alkaline earth oxide/cerium oxide, other alkalioxide(s) or alkaline earth oxide(s)/cerium oxide, and PGM/cerium oxide.

PNA Material with PGM Compositions

In some embodiments, the PNA material is loaded with about 1 g/L toabout 20 g/L of PGM. In another embodiment, the PNA material is loadedwith about 1 g/L to about 15 g/L of PGM. In another embodiment, the PNAmaterial is loaded with about 6.0 g/L and less of PGM. In anotherembodiment, the PNA material is loaded with about 5.0 g/L and less ofPGM. In another embodiment, the PNA material is loaded with about 4.0g/L and less of PGM. In another embodiment, the PNA material is loadedwith about 3.0 g/L and less of PGM. In another embodiment, the PNAmaterial is loaded with about 2 g/L to about 4 g/L Pd. In anotherembodiment, the PNA material is loaded with about 3 g/L Pd. In anotherembodiment, the PNA material is loaded with about 3 g/L to about 15 g/LRu. In another embodiment, the PNA material is loaded with about 5 g/Lto about 6 g/L Ru.

The PNA material can include support particles impregnated with PGM. Insome embodiments, PGM may be added to support particles using wetchemistry techniques. In some embodiments, PGM may be added to supportparticles using incipient wetness. In some embodiments, PGM may be addedto support particles using plasma based methods such as nano-on-nano toform PNA composite nanoparticles. In some embodiments, these PNAcomposite nanoparticles are added to carrier particles to form NNm PNAparticles or are embedded within carrier particles to form NNiM PNAparticles. As such, the PGM on support particles can include micro-PGMon micron support particles, nano-PGM on micron support particles, PNAnano-on-nano particles, PNA NNm particles, PNA NNiM particles, or PNAhybrid NNm/wet-chemistry particles described above. In some embodiments,the micron-sized particles of the PGM NNm particles can be themicron-sized supports impregnated with the alkali oxides or alkalineearth oxides. In some embodiments, the micron-sized particles of the PGMNNm particles can be impregnated with alkali oxides or alkaline earthoxides. In some embodiments, the alkali oxides or alkaline earth oxidesand PGM are on the same support particle. In other embodiments, thealkali oxides or alkaline earth oxides and PGM are on different supportparticles.

In some embodiments, the support particles of the PNA material maycontain platinum. In some embodiments, the support particles of the PNAmaterial may contain rhodium. In some embodiments, the support particlesof the PNA material may contain palladium. In some embodiments, thesupport particles of the PNA material may contain ruthenium. In someembodiments, the support particles of the PNA material may contain amixture of platinum and palladium. For example, the support particles ofthe PNA material may contain a mixture of 2:1 to 100:1 platinum topalladium. In some embodiments, the support particles of the PNAmaterial may contain a mixture of 2:1 to 75:1 platinum to palladium. Insome embodiments, the support particles of the PNA material may containa mixture of 2:1 to 50:1 platinum to palladium. In some embodiments, thesupport particles of the PNA material may contain a mixture of 2:1 to25:1 platinum to palladium. In some embodiments, the support particlesof the PNA material may contain a mixture of 2:1 to 15:1 platinum topalladium. In some embodiments, the support particles of the PNAmaterial may contain a mixture of 2:1 to 10:1 platinum to palladium. Insome embodiments, the support particles of the PNA material may containa mixture of 2:1 platinum to palladium, or approximately 2:1 platinum topalladium. In some embodiments, the support particles may contain amixture of 2:1 to 20:1 platinum to palladium. In some embodiments, thesupport particles may contain a mixture of 5:1 to 15:1 platinum topalladium. In some embodiments, the support particles may contain amixture of 8:1 to 12:1 platinum to palladium. In some embodiments, thesupport particles may contain a mixture of 10:1 platinum to palladium,or approximately 10:1 platinum to palladium. In some embodiments, thesupport particles may contain a mixture of 2:1 to 8:1 platinum topalladium. In some embodiments, the support particles may contain amixture of 3:1 to 5:1 platinum to palladium. In some embodiments, thesupport particles may contain a mixture of 4:1 platinum to palladium, orapproximately 4:1 platinum to palladium.

In some embodiments, the PNA material can include NNm™ particlescomprising composite PNA nanoparticles. In other embodiments, the PNAmaterial can include NNiM particle comprising composite PNAnanoparticles. The PGM NNm's micro-sized components can further beimpregnated with alkali oxides or alkaline earth oxides to form a PNAmaterial. The micro-sized component of the PGM NNm can be cerium oxide.As described above, in all embodiments, the cerium oxide can includezirconium oxide, lanthanum, lanthanum oxide, yttrium oxide, or acombination thereof. In some embodiments, the cerium oxide includes 86wt % cerium oxide, 10 wt % zirconium oxide, and 4 wt % lanthanum and/orlanthanum oxide. In addition, micro-sized cerium oxide that has beenimpregnated with alkali oxides or alkaline earth oxides can be used asthe micro-sized component of the NNm and NNiM particles.

The following discussion will be exemplified using NNm™ particles, butapplies equally well to NNiM particles. The composite nanoparticle mayinclude one or more nanoparticles attached to a support nanoparticle toform a “nano-on-nano” composite nanoparticle that may trap or storeNO_(x) gases. Platinum group metals may be used to prepare the compositenanoparticle. In certain embodiments, the composite nanoparticle maycontain palladium. In other embodiments, the composite nanoparticle maycontain ruthenium. A suitable support nanoparticle for the compositenanoparticles includes, but is not limited to, nano-sized cerium oxide(which can include zirconium oxide, lanthanum, lanthanum oxide, yttriumoxide, or a combination thereof).

Each composite nanoparticle may be supported on a single supportnanoparticle or each support nanoparticle may include one or morecomposite nanoparticles. The composite nanoparticles on the supportnanoparticle may include palladium, ruthenium, or a mixture thereof. Insome embodiments, palladium is used alone. In other embodiments,ruthenium may be used alone. In further embodiments, platinum may beused in combination with palladium. For example, the supportnanoparticle may contain a mixture of 2:1 to 100:1 platinum topalladium. In some embodiments, the support nanoparticle may contain amixture of 2:1 to 75:1 platinum to palladium. In some embodiments, thesupport nanoparticle may contain a mixture of 2:1 to 50:1 platinum topalladium. In some embodiments, the support nanoparticle may contain amixture of 2:1 to 25:1 platinum to palladium. In some embodiments, thesupport nanoparticle may contain a mixture of 2:1 to 15:1 platinum topalladium. In some embodiments, the support nanoparticle may contain amixture of 2:1 to 10:1 platinum to palladium. In some embodiments, thesupport nanoparticle may contain a mixture of 2:1 platinum to palladium,or approximately 2:1 platinum to palladium. In some embodiments, thesupport particles may contain a mixture of 2:1 to 20:1 platinum topalladium. In some embodiments, the support particles may contain amixture of 5:1 to 15:1 platinum to palladium. In some embodiments, thesupport particles may contain a mixture of 8:1 to 12:1 platinum topalladium. In some embodiments, the support particles may contain amixture of 10:1 platinum to palladium, or approximately 10:1 platinum topalladium. In some embodiments, the support particles may contain amixture of 2:1 to 8:1 platinum to palladium. In some embodiments, thesupport particles may contain a mixture of 3:1 to 5:1 platinum topalladium. In some embodiments, the support particles may contain amixture of 4:1 platinum to palladium, or approximately 4:1 platinum topalladium.

The composite nanoparticles for use as components of the PNA materialcan be produced by plasma-based methods as described above. Platinumgroup metals (such as ruthenium, palladium, or a mixture thereof) can beintroduced into the plasma reactor as a fluidized powder in a carriergas stream. The resulting nano-on-nano particles have similar properties(i.e., diameter or grain size) to that of the oxidative nano-on-nanoparticles and reductive nano-on-nano particles. In one embodiment, forNO_(x) adsorbing composite nanoparticles, ruthenium, palladium, or amixture of palladium and platinum, can be deposited on nano-sized ceriumoxide.

To prepare a PNA material that comprises a nano-on-nano-on-microparticle (NNm), a dispersion of the composite nanoparticles may beapplied to porous, micron-sized cerium oxide or aluminum oxide. Afterthe composite nanoparticles are applied to the micron-sized ceriumoxide, the micron-sized cerium oxide may be impregnated with alkalioxide or alkaline earth oxide nanoparticles. In some embodiments, theNNm particles are combined with separate alkali oxides or alkaline earthoxides on cerium oxide supports to form the PNA material. Themicron-sized cerium oxide may contain zirconium oxide. In someembodiments, the micron-sized cerium oxide is substantially free ofzirconium oxide. In other embodiments, the micron-sized cerium oxidecontains up to 100% zirconium oxide. In one embodiment, the nanoparticleis a PGM. In one embodiment, the PGM is platinum, palladium, or amixture thereof. In another embodiment, the PGM is ruthenium. In otherembodiments, the nanoparticle is a non-PGM. In some embodiments, thenon-PGM is tungsten, molybdenum, niobium, manganese, or chromium.

The micron-sized carrier particles, impregnated with the compositenanoparticles may be prepared as described above for theNano-on-Nano-on-Micro particles.

In some embodiments, the PNA material comprises multiple types ofparticles comprising micron-sized cerium oxide particles impregnatedwith alkali oxide or alkaline earth oxide particles, and separate NNm orNNiM particles comprising ruthenium, platinum, palladium, or mixturesthereof.

In some instances, the weight ratio of nano-sized Ru, Pt, Pd, orPt/Pd:nano-sized cerium oxide is about 1%:99% to about 40%:60%. In oneembodiment, the weight ratio of nano-sized Ru, Pt, Pd, orPt/Pd:nano-sized cerium oxide is about 10%:90%. In addition, the Ru, Pt,Pd, or Pt/Pd can include their oxides, such as ruthenium oxide.

The PNA NNm™ particles may contain from about 0.1% to 6% Pd, Ru, orruthenium oxide by weight, or in another embodiment from about 0.5% to3.5% by weight, or in another embodiment, about 1% to about 2.5% byweight, or in another embodiment about 2% to about 3% by weight, or inanother embodiment, about 2.5% by weight, of the total mass of the NNm™particle. The NNm™ particles can then be used for formulations forcoating substrates, where the coated substrates may be used in catalyticconverters.

In further embodiments, the NNm™ particles may be comprised of metalssuch as W, Mo, Nb, Mn, or Cr produced using the plasma-based methodsdescribed above.

Substrates

The initial substrate is preferably a catalytic converter substrate thatdemonstrates good thermal stability, including resistance to thermalshock, and to which the described washcoats can be affixed in a stablemanner. Suitable substrates include, but are not limited to, substratesformed from cordierite or other ceramic materials, and substrates formedfrom metal. The substrate may be a honeycomb structure. The substratesmay include a grid array structure or coiled foil structure, whichprovide numerous channels and result in a high surface area. The highsurface area of the coated substrate with its applied washcoats in thecatalytic converter provides for effective treatment of the exhaust gasflowing through the catalytic converter. A corner fill layer, or abuffer layer or adhesion layer such as a thin Boehmite layer, may beapplied to the substrate prior to applying any of the active washcoatlayers, but is not required.

Washcoat Compositions and Layers Using PNA Material: Application toSubstrates

Washcoat formulations comprising the PNA material may be used to provideone or more layers on substrates used for catalysis, such as a catalyticconverter substrate. Additional washcoats can also be used for improvedperformance. In some embodiments, the washcoat formulations may includetwo or more different washcoats formulations that allow for theseparation of one or more washcoat layers containing high concentrationsof zeolite particles from one or more washcoat layers containingplatinum group metal catalyst, such as the NNm particles describedabove, on a catalytic converter substrate. The formulations may be usedto form washcoat layers and catalytic converter substrates that includereduced amounts of platinum group metals and offer better performancewhen compared to previous washcoat layers and formulations and catalyticconverter substrates.

Many of the washcoat compositions disclosed herein can include boehmite.Boehmite can be added to the washcoat compositions as a binder and isconverted to aluminum oxide upon calcination.

Some embodiments of washcoat formulations may be formulated to form oneor more of the following basic washcoat layer configurations:

Substrate-Catalytic Layer-PNA Layer-Zeolite Layer (S-C-P-Z)

Substrate-Catalytic Layer-Zeolite Layer-PNA Layer (S-C-Z-P)

Substrate-PNA Layer-Zeolite Layer-Catalytic Layer (S-P-Z-C)

Substrate-PNA Layer-Catalytic Layer-Zeolite Layer (S-P-C-Z)

Substrate-Zeolite Layer-PNA Layer-Catalytic Layer (S-Z-P-C)

Substrate-Zeolite Layer-Catalytic Layer-PNA Layer (S-Z-C-P)

Substrate-Catalytic Layer-(PNA/Zeolite Layer) (S-C-PZ)

Substrate-(PNA/Zeolite Layer)-Catalytic Layer (S-PZ-C)

Substrate-(PNA/Zeolite/Catalytic Layer) (S-PZC)

Substrate-PNA Layer (S-P)

Any of the above configurations can contain a Corner Fill Layer (F) thatmay be used to fill corners of the substrate prior to deposition ofadditional layers. In addition, any of the above configurations can havemore than one of any layer. In addition, any of the above configurationsmay remove one or more than one layer. In the configurations above: 1)the Substrate (S) may be any substrate suitable for use in a catalyticconverter, 2) the Zeolite Layer (Z) is a washcoat layer that includeszeolite particles, 3) the Catalytic Layer (C) is a washcoat layer thatincludes catalytically active particles (there can be more than onecatalytic layer such as a reductive catalytic layer and an oxidativecatalytic layer), 4) the PNA Layer (P) is a washcoat layer that includesa NO_(x) adsorber, 5) the PNA/Zeolite Layer (PZ) is a washcoat layerthat includes a NO_(x) adsorber and zeolites and 6) thePNA/Zeolite/Catalytic Layer (PZC) which is a washcoat layer thatincludes an NO_(x) adsorber, zeolites, and catalytically activeparticles.

It should be noted that, in some embodiments, additional washcoat layerscan be disposed under, over, on top of, or between any of the washcoatlayers indicated in these basic configurations; that is, further layerscan be present on the catalytic converter substrate in addition to theones listed in the configurations above. When a layer (layer Y) is saidto be formed “on top of” another layer (layer X), either no additionallayers, or any number of additional layers (layer(s) A, B, C, etc.) canbe formed between the two layers X and Y. For example, if layer Y issaid to be formed on top of layer X, this can refer to a situation wherelayer X can be formed, then layer A can be formed immediately atop layerX, then layer B can be formed immediately atop layer A, then layer Y canbe formed immediately atop layer B. Alternatively, if layer Y is said tobe formed on top of layer X, this can refer to a situation where layer Ycan be deposited directly on top of layer X with no intervening layersbetween X and Y. For the specific situation where no intervening layersare present between layer X and layer Y, layer Y is said to be formedimmediately atop layer X, or equivalently, layer Y is said to be formeddirectly on top of layer X.

In other embodiments, additional washcoat layers are not applied; thatis, the washcoats listed in the configurations above are the onlywashcoats present on the catalytic converter substrate. In otherembodiments, the washcoats listed in the configurations above might havea layer not present (that is, a layer may be omitted).

In the following washcoat descriptions, the composite nanoparticles aredescribed as a component of the NNm™ particles for illustrative purposesonly. However, the composite nanoparticles could equally well be acomponent of the NNiM particles. In the following descriptions, thepercentages of the components of the washcoat compositions are providedin terms of the amount of solids present in the washcoat compositions,as the washcoat compositions can be provided in an aqueous suspensionor, in some instances, as dry powder. The “layers” refers to thecorresponding washcoat composition after it has been applied to thesubstrate, dried, and calcined.

General Washcoat Preparation Procedure

Washcoats are prepared by suspending the designated materials in anaqueous solution, adjusting the pH to between about 2 and about 7, tobetween about 3 and about 5, or to about 4, and adjusting the viscosity,if necessary, using cellulose, cornstarch, or other thickeners, to avalue between about 300 cP to about 1200 cP.

The washcoat is applied to the substrate (which may already have one ormore previously-applied washcoats) by coating the substrate with theaqueous solution, blowing excess washcoat off of the substrate (andoptionally collecting and recycling the excess washcoat blown off of thesubstrate), drying the substrate, and calcining the substrate.

General Drying and Calcining of Washcoats

Once each washcoat is applied to the substrate (which may or may nothave already been coated with previous substrates), excess washcoat isblown off and the residue collected and recycled. The washcoat may thenbe dried. Drying of the washcoats can be performed at room temperatureor elevated temperature (for example, from about 30° C. to about 95° C.,preferably about 60° C. to about 70° C.), at atmospheric pressure or atreduced pressure (for example, from about 1 pascal to about 90,000pascal, or from about 7.5 mTorr to about 675 Torr), in ambientatmosphere or under an inert atmosphere (such as nitrogen or argon), andwith or without passing a stream of gas over the substrate (for example,dry air, dry nitrogen gas or dry argon gas). In some embodiments, thedrying process is a hot-drying process. A hot drying process includesany way to remove the solvent at a temperature greater than roomtemperature, but at a temperature below a standard calciningtemperature. In some embodiments, the drying process may be a flashdrying process, involving the rapid evaporation of moisture from thesubstrate via a sudden reduction in pressure or by placing the substratein an updraft of warm air. It is contemplated that other dryingprocesses may also be used.

After drying the washcoat onto the substrate, the washcoat may then becalcined onto the substrate. Calcining takes place at elevatedtemperatures, such as from 400° C. to about 700° C., preferably about500° C. to about 600° C., more preferably at about 540° C. to about 560°C. or at about 550° C. Calcining can take place at atmospheric pressureor at reduced pressure (for example, from about 1 pascal to about 90,000pascal, or about 7.5 mTorr to about 675 Torr), in ambient atmosphere orunder an inert atmosphere (such as nitrogen or argon), and with orwithout passing a stream of gas over the substrate (for example, dryair, dry nitrogen gas, or dry argon gas).

Corner-Fill Washcoat Compositions and Layers

The corner fill washcoat layer (F) may be a relatively inexpensivelayer, which can be applied to the substrate to fill up the “corners”and other areas of the substrate where exhaust gases are unlikely topenetrate in significant amounts. Preferably, this layer does notinclude any PGM, zeolites, or PNA material. The corner fill layer isschematically diagrammed in FIG. 4, which shows a single rectangularchannel 400 in a substrate coated in the S-F-C-P-Z configuration. Thewall 410 of the substrate channel has been coated with corner-fillwashcoat layer 420, then catalyst-containing washcoat layer 430, thenPNA material-containing washcoat layer 440, then zeoliteparticle-containing washcoat layer 450. When the coated substrate isoperating in the catalytic converter, exhaust gases pass through thelumen 460 of the channel. The corners of the channel (one of which, 470,is indicated by an arrow) have a relatively thick coating, and exhaustgases will be less likely to contact those regions. In, for example, theS-C-P-Z configuration, the layers 420, 430, and 440 would be a singlelayer, the catalyst-containing washcoat layer, and significant amountsof expensive platinum group metal would be located in the corners (suchas 470) where they are relatively inaccessible for catalysis. Thus,while the S-C-P-Z configuration can be used, it may not be ascost-effective. The corner fill washcoat layer may not provide anequivalent cost savings in the S-Z-P-C configuration, for example, aszeolites are relatively inexpensive.

While a rectangular shape is shown for illustration, an equivalentanalysis holds for any substrate with polygonal-shaped channels, or anysubstrate with channels that are not essentially cylindrical. Forsubstrates with essentially cylindrical channels, which by definition donot have corners, a corner-fill washcoat may not be necessary foreconomic reasons (although it may still be applied for other reasons,such as to adjust the diameter of the channels).

The corner-fill washcoat compositions may comprise aluminum oxideparticles (i.e., alumina). Aluminum-oxide particles such as MI-386material from Grace Davison, or the like, for example, can be used. Thesize of the aluminum oxide particles is generally above about 0.2microns, preferably above about 1 micron. The solids content of thecorner-fill washcoat include about 80% to about 98% by weight porousalumina (MI-386 or the like) and about 20% to about 2% boehmite, such asabout 90% to 97% alumina and about 10% to 3% boehmite, or about 95% to97% alumina and about 5% to about 3% boehmite, such as a corner-fillwashcoat including about 97% porous alumina and about 3% boehmite.

In some embodiments, each of the aluminum oxide particles orsubstantially each of the aluminum oxide particles in the corner-fillwashcoat composition have a diameter of approximately 0.2 microns toapproximately 8 microns, such as about 4 microns to about 6 microns. Insome embodiments, the aluminum oxide particles in the corner-fillwashcoat composition have an average grain size of approximately 0.2microns to approximately 8 microns, such as about 4 microns to about 6microns. In some embodiments, at least about 75%, at least about 80%, atleast about 90%, or at least about 95% of the aluminum oxide particlesin the corner-fill washcoat composition have a particle size fallingwithin the range of approximately 0.2 microns to approximately 8microns, such as within the range of about 4 microns to about 6 microns.After a washcoat layer has been applied to a substrate, it may be dried,then calcined, onto the substrate. The corner-fill washcoat may beapplied in a thickness of from about 30 g/l up to about 100 g/l; atypical value may be about 50 g/l.

Zeolite Washcoat Compositions and Zeolite Layers

Zeolite particles may be used to trap hazardous gases, such ashydrocarbons, carbon monoxide, and nitrogen oxides, during cold start ofan internal combustion engine. The Zeolite Layer is a washcoat layer,deposited using a washcoat composition that includes a higher percentageof zeolite than the Catalytic layer. In some embodiments, the ZeoliteLayer and washcoat includes no catalytically active particles.

In some embodiments, the zeolite layer and washcoat compositionscomprise, consist essentially of, or consist of zeolite particles,boehmite particles, and metal-oxide particles. The metal-oxide particlesare preferably porous. The metal-oxide particles may be aluminum-oxideparticles (e.g., MI-386 from Grace Davison or the like). Thealuminum-oxide particles may be porous. Different configurations of theweight concentrations of the zeolite particles, boehmite particles, andmetal-oxide particles may be employed. In the following descriptions,the percentages of the components of the washcoat compositions areprovided in terms of the amount of solids present in the washcoatcompositions, as the washcoat compositions can be provided in an aqueoussuspension or, in some instances, as dry powder. The zeolite layerrefers to the zeolite washcoat composition after it has been applied tothe substrate, dried, and calcined.

In some embodiments, the zeolite particles comprise at least 50%,comprise more than about 50%, or comprise about 50% to about 100% byweight of the combination of zeolite particles, boehmite particles, andmetal-oxide particles in the zeolite washcoat composition or zeolitelayer. In some embodiments, the zeolite particles make up approximately60% to approximately 80%, for example, approximately 65% toapproximately 70% or approximately 70% to approximately 80%, by weightof the combination of zeolite particles, boehmite particles, andmetal-oxide particles in the zeolite particle-containing washcoatcomposition or zeolite layer. In some embodiments, the zeolite particlesin the zeolite particle-containing washcoat composition or zeolite layereach have a diameter of approximately 0.2 microns to approximately 8microns, such as about 4 microns to about 6 microns, prior to coating.In some embodiments, at least about 75%, at least about 80%, at leastabout 90%, or at least about 95% of the zeolite particles in the zeoliteparticle-containing washcoat composition or zeolite layer have aparticle size falling with the range of approximately 0.2 microns toapproximately 8 microns, such as within the range of about 4 microns toabout 6 microns. In some embodiments, the boehmite particles make upapproximately 2% to approximately 5% by weight of the combination ofzeolite particles, boehmite particles, and metal-oxide particles in thezeolite particle-containing washcoat composition or zeolite layer. Insome embodiments, the boehmite particles make up approximately 3% byweight of the combination of zeolite particles, boehmite particles, andmetal-oxide particles in the zeolite particle-containing washcoatcomposition or zeolite layer. In some embodiments, the metal-oxideparticles make up approximately 15% to approximately 38%, for example,approximately 15% to approximately 30%, approximately 17% toapproximately 23% or approximately 17% to approximately 22%, by weightof the mixture of zeolite particles, metal-oxide particles, and boehmiteparticles in the zeolite particle-containing washcoat composition orzeolite layer. In some embodiments, the metal-oxide particles make upapproximately 15% to approximately 23% by weight of the mixture ofzeolite particles, metal-oxide particles, and boehmite particles in thezeolite particle-containing washcoat composition or zeolite layer. Insome embodiments, the metal-oxide particles make up approximately 25% toapproximately 35% by weight of the mixture of zeolite particles,metal-oxide particles, and boehmite particles in the zeoliteparticle-containing washcoat composition or zeolite layer. In someembodiments, the zeolite-particle containing washcoat composition orzeolite layer contains about 3% boehmite particles, about 67% zeoliteparticles, and about 30% porous aluminum-oxide particles.

In some embodiments, the zeolite particle-containing washcoatcomposition or zeolite layer does not comprise any platinum groupmetals. As discussed above, the six platinum group metals are ruthenium,rhodium, palladium, osmium, iridium, and platinum. In some embodiments,the zeolite particle-containing washcoat composition or zeolite layer ischaracterized by a substantial absence of any platinum group metals. Insome embodiments, the zeolite particle-containing washcoat compositionor zeolite layer is 100% free of any platinum group metals. In someembodiments, the zeolite particle-containing washcoat composition orzeolite layer is approximately 100% free of any platinum group metals.In some embodiments, the zeolite particle-containing washcoatcomposition or zeolite layer does not comprise any catalytic particles.In some embodiments, the zeolite particle-containing washcoatcomposition or zeolite layer is characterized by a substantial absenceof any catalytic particles. In some embodiments, the zeoliteparticle-containing washcoat composition or zeolite layer is 100% freeof any catalytic particles. In some embodiments, the zeoliteparticle-containing washcoat composition or zeolite layer isapproximately 100% free of any catalytic particles.

In some embodiments, the zeolite particle-containing washcoatcomposition or zeolite layer may include by weight about 2% to about 5%boehmite particles, about 60% to about 80% zeolite particles, and therest porous aluminum-oxide particles (i.e., about 15% to about 38%). Inone embodiment, the zeolite particle-containing washcoat composition orzeolite layer includes by weight about 2% to about 5% boehmiteparticles, about 75% to about 80% zeolite particles, and the rest porousaluminum-oxide particles (i.e., about 15% to about 23%). In anotherembodiments, the zeolite particle-containing washcoat composition orzeolite layer includes by weight about 2% to about 5% boehmiteparticles, about 65% to about 70% zeolite particles, and the rest porousaluminum-oxide particles (i.e., about 25% to about 33%). In someembodiment, the zeolite-particle containing washcoat composition orzeolite layer contains about 3% boehmite particles, about 67% zeoliteparticles, and about 30% porous aluminum-oxide particles. In someembodiments, the zeolite particle-containing washcoat composition orzeolite layer does not contain any catalytic material. In someembodiments, the zeolite particle-containing washcoat composition orzeolite layer does not contain any platinum group metals.

In some embodiments, the zeolite particle-containing washcoatcomposition or zeolite layer may include PNA material.

In some embodiments, the zeolite particle-containing washcoatcomposition is mixed with water and acid, such as acetic acid, prior tocoating of a substrate with the zeolite particle-containing washcoatcomposition, thereby forming an aqueous mixture of the zeoliteparticle-containing washcoat composition, water, and acid. This aqueousmixture of the zeolite particle-containing washcoat composition, water,and acid may then be applied to the substrate (where the substrate mayor may not already have other washcoat layers applied to it). In someembodiments, the pH of this aqueous mixture may be adjusted to a pHlevel of about 2 to about 7 prior to it being applied to the substrate.In some embodiments, the pH of this aqueous mixture may be adjusted to apH level of about 4 prior to it being applied to the substrate.

In some embodiments, the zeolite layer (that is, the zeoliteparticle-containing washcoat composition applied to the substrate, orthe zeolite-particle containing washcoat layer) has a thickness ofapproximately 25 g/l to approximately 90 g/l (grams/liter),approximately 50 g/l to approximately 80 g/l, or approximately 70 toapproximately 90 g/l. In some embodiments, the zeolite layer has athickness of approximately 50 g/l, 60 g/l, 70 g/l, 80 g/l, or 90 g/l. Insome embodiments, the zeolite layer has a thickness of approximately 80g/l.

In some embodiments, where the zeolite layer is applied on top of thecatalyst-containing layer (i.e., the catalyst-containing layer is closerto the substrate than the zeolite layer), the zeolite layer has athickness of about 70 g/l to about 90 g/l.

In some embodiments, where the zeolite layer is applied under thecatalyst-containing layer (i.e., the zeolite layer is closer to thesubstrate than the catalyst-containing layer), the zeolite layer has athickness of about 50 g/l to about 80 g/l.

Catalytically Active Particle-Containing Washcoat Compositions andCatalytically Active Layers

The catalyst-containing washcoat composition and the catalyst layer onthe substrate, contains catalytically active material and can be formedin a variety of ways. In addition, there can be more than one catalystlayer on the substrate. For example, there can be an oxidative catalystlayer and a reductive catalyst layer. Examples of catalytically activeparticle washcoats and additional washcoats are disclosed in U.S.Provisional Application 61/894,346, which has been incorporated byreference in its entirety.

Preferred catalysts are platinum group metals (PGMs). Platinum groupmetals are the metals platinum, palladium, rhodium, ruthenium, osmium,and iridium. The individual metals can be used as catalysts, and variouscombinations of metals can also be used. For example, the NNmmicron-sized particles described above are preferably used. Thecatalytically active particles may have composite nano-particles, wherethe composite nanoparticles have a population of support nano-particlesbearing catalytic nano-particles comprising platinum and a population ofsupport nano-particles bearing catalytic nano-particles comprisingpalladium. The micron-sized support particles bearing compositeparticles may include support nano-particles bearing catalyticnano-particles, where the catalytic nanoparticles include aplatinum/palladium alloy, such as a 2:1 Pt/Pd ratio (weight/weight). Insome embodiments, the micron-sized carrier particles are alumina(aluminum oxide) particles on which a plurality of compositenano-particles are attached, the composite nano-particles comprising asupport nano-particle and a catalytic nano-particle. In one embodiment,MI-386 alumina powder from Grace Davison is used as the micron-sizedalumina particles.

In the following descriptions, the percentages of the components of thewashcoat compositions are provided in terms of the amount of solidspresent in the washcoat compositions, as the washcoat compositions canbe provided in an aqueous suspension or, in some instances, as drypowder. The catalyst layer (or catalyst-containing layer) refers to thecatalyst-containing washcoat composition after it has been applied tothe substrate, dried, and calcined.

The previously described zeolite-particle containing washcoatcompositions and zeolite-particle containing layers are preferably freeof, or in an alternative embodiment, substantially free of, catalyticparticles or platinum group metals. It is preferred that thecatalyst-containing washcoat compositions and layers are free of, orsubstantially free of, zeolites. However, in some embodiments, thecatalyst-containing washcoat compositions and catalyst layers cancontain an amount of zeolites, such as up to about 20%, up to about 10%,or up to about 5% of the total solids in the catalyst-containingwashcoat compositions or catalyst-containing layers.

In some embodiments, the catalyst-containing washcoat compositionfurther includes “spacer” or “filler” particles, where the spacerparticles may be ceramic, metal oxide, or metallic particles. In someembodiments, the spacer particles may be silica, alumina, boehmite, orzeolite particles, or any mixture of the foregoing, such as boehmiteparticles, silica particles and zeolite particles in any proportion.

In some embodiments where the catalyst-containing washcoat compositionand catalyst layers are substantially free of zeolites and PNA material,the catalyst-containing washcoat composition comprises, consistsessentially of, or consists of silica particles, alumina/sealantparticles with or without BaO, boehmite particles, and NNm particles. Insome embodiments, the NNm particles make up between approximately 35% toapproximately 95% by weight of the combination of the NNm particles, theboehmite particles, and the alumina/sealant and cerium oxide particlesin the catalyst-containing washcoat composition or catalyst-containinglayer. In some embodiments, the NNm particles make up betweenapproximately 40% to approximately 92% by weight of the combination ofthe NNm particles, the boehmite particles, and the alumina/sealant andceria particles in the catalyst-containing washcoat composition orcatalyst-containing layer. In some embodiments, the NNm particles makeup between approximately 60% to approximately 95% by weight of thecombination of the NNm particles, the boehmite particles, and thealumina/sealant and ceria particles in the catalyst-containing washcoatcomposition or catalyst-containing layer. In some embodiments, the NNmparticles make up between approximately 80% to approximately 95% byweight of the combination of the NNm particles, the boehmite particles,and the alumina/sealant and ceria particles in the catalyst-containingwashcoat composition or catalyst-containing layer. In some embodiments,the NNm particles make up between approximately 80% to approximately 92%by weight of the combination of the NNm particles, the boehmiteparticles, and the alumina/sealant and ceria particles in thecatalyst-containing washcoat composition or catalyst-containing layer.In some embodiments, the NNm particles make up approximately 92% byweight of the combination of the NNm particles, the boehmite particles,and the alumina/sealant and ceria particles in the catalyst-containingwashcoat composition or catalyst-containing layer.

In some embodiments, the NNm™ particles make up between approximately35% to approximately 75% by weight of the combination of the NNmparticles, the boehmite particles, and the alumina/sealant and ceriaparticles. In some embodiments, the NNm™ particles make up betweenapproximately 40% to approximately 60% by weight of the combination ofthe NNm particles, the boehmite particles, and the alumina/sealant andceria particles. In some embodiments, the NNm™ particles make up betweenapproximately 45% to approximately 55% by weight of the combination ofthe NNm particles, the boehmite particles, and the alumina/sealant andceria particles. In some embodiments, the NNm™ particles make up about50% by weight of the combination of the NNm particles, the boehmiteparticles, and the alumina/sealant and ceria particles.

In some embodiments, the percentage of platinum group metal in thecatalyst-containing washcoat composition and catalyst layers ranges frombetween about 0.25% to about 4%, about 0.5% to about 4%, about 0.5% toabout 3%, about 1% to about 3%, about 1% to about 2%, about 1% to about1.5%, about 1.5% to about 3%, about 1.5% to about 2.5%, about 1.5% toabout 2%, about 2% to about 3%, about 2.5% to about 3%, or about 2% toabout 2.5%. In some embodiments, the percentage of platinum group metalin the catalyst-containing washcoat composition and catalyst layers isabout 0.5%, about 0.75%, about 1%, about 1.25%, about 1.5%, about 1.75%,about 2%, about 2.25%, about 2.5%, about 2.75%, or about 3%. In someembodiments, the percentage of platinum group metal in thecatalyst-containing washcoat composition and catalyst layers is about2.3%.

In some embodiments, the NNm™ particles make up between approximately50% to approximately 95% by weight of the combination of the NNmparticles, the boehmite particles, and the alumina/sealant and ceriaparticles. In some embodiments, the NNm™ particles make up betweenapproximately 60% to approximately 90% by weight of the combination ofthe NNm particles, the boehmite particles, and the alumina/sealant andceria particles. In some embodiments, the NNm™ particles make up betweenapproximately 75% to approximately 85% by weight of the combination ofthe NNm particles, the boehmite particles, and the alumina/sealant andceria particles. In some embodiments, the NNm™ particles make up about80% by weight of the combination of the NNm particles, the boehmiteparticles, and the alumina/sealant and ceria particles. In someembodiments, the catalytically active particle in the NNm™ particles isrhodium at a loading of about 0.3-2 wt % in the NNm™ particles. In someembodiments, the catalytically active particle in the NNm™ particles isrhodium at a loading of about 0.3-1 wt % in the NNm™ particles. In someembodiments, the catalytically active particle in the NNm™ particles isrhodium at a loading of about 0.3-0.5 wt % in the NNm™ particles. In oneembodiment, the catalytically active particle in the NNm™ particles isrhodium at a loading of about 0.3 wt % in the NNm™ particles. In anotherembodiment, the catalytically active particle in the NNm™ particles isrhodium at a loading of about 0.4 wt % in the NNm™ particles. Otherloadings described previously may also be used.

In some embodiments, the silica particles make up approximately 20% orless by weight of the combination of the NNm particles, the boehmiteparticles, and the alumina/sealant and ceria particles in thecatalyst-containing washcoat composition or catalyst-containing layer;or the silica particles make up approximately 10% or less by weight ofthe combination of the NNm particles, the boehmite particles, and thealumina/sealant and ceria particles in the catalyst-containing washcoatcomposition or catalyst-containing layer; in further embodiments, thesilica particles make up approximately 5% or less by weight of thecombination of the NNm particles, the boehmite particles, and thealumina/sealant and ceria particles in the catalyst-containing washcoatcomposition or catalyst-containing layer. In various embodiments, thesilica particles make up approximately 1% to approximately 20%,approximately 1% to approximately 10%, approximately 1% to approximately5%, about 20%, about 10%, about 5%, or about 1% by weight of thecombination of the NNm particles, the boehmite particles, and thealumina/sealant and ceria particles in the catalyst-containing washcoatcomposition or catalyst-containing layer.

In some embodiments, the boehmite particles make up approximately 2% toapproximately 5% by weight of the combination of the NNm particles, theboehmite particles, and the alumina/sealant and ceria particles in thecatalyst-containing washcoat composition or catalyst-containing layer.In some embodiments, the boehmite particles make up approximately 3% byweight of the combination of the NNm particles, the boehmite particles,and the alumina/sealant and ceria particles in the catalyst-containingwashcoat composition or catalyst-containing layer.

In some embodiments, the alumina filler/sealant particles make upbetween approximately 30% to approximately 70% by weight of thecombination of the NNm particles, the boehmite particles, and thealumina/sealant and ceria particles. In some embodiments, the aluminafiller/sealant particles make up between approximately 40% toapproximately 60% by weight of the combination of the NNm particles, theboehmite particles, and the alumina/sealant and ceria particles. In someembodiments, the alumina filler/sealant particles make up betweenapproximately 45% to approximately 55% by weight of the combination ofthe NNm particles, the boehmite particles, and the alumina/sealant andceria particles. In some embodiments, the alumina filler/sealantparticles make up about 50% by weight of the combination of the NNmparticles, the boehmite particles, and the alumina/sealant and ceriaparticles. The alumina filler/sealant particles may be porouslanthanum-stabilized alumina, for example MI-386. In some embodiments, adifferent filler particle may be used in place of some or all of thealumina particles.

In some embodiments, the alumina filler/sealant particles make upbetween approximately 5% to approximately 40% by weight of thecombination of the NNm particles, the boehmite particles, and thealumina/sealant and ceria particles. In some embodiments, the aluminafiller/sealant particles make up between approximately 10% toapproximately 30% by weight of the combination of the NNm particles, theboehmite particles, and the alumina/sealant and ceria particles. In someembodiments, the alumina filler/sealant particles make up betweenapproximately 15% to approximately 20% by weight of the combination ofthe NNm particles, the boehmite particles, and the alumina/sealant andceria particles. In some embodiments, the alumina filler/sealantparticles make up about 17% by weight of the combination of the NNmparticles, the boehmite particles, and the alumina/sealant and ceriaparticles. The alumina filler/sealant particles may be porouslanthanum-stabilized alumina, for example MI-386. In some embodiments, adifferent filler particle may be used in place of some or all of thealumina particles.

In the washcoat, from 0 to 100% of the alumina filler/sealant particlesmay be alumina impregnated with nano-sized BaO particles, alumina mixedwith micron-sized BaO particles, or both alumina impregnated withnano-sized BaO particles and admixed with micron-sized BaO particles. Insome embodiments, from 1 wt %-100 wt %, from 20 wt %-80 wt %, or from 30wt %-60 wt % micron-sized BaO may be used in place ofnon-BaO-impregnated alumina. In some embodiments, a 50:50 mixture ofregular MI-386 and BaO-impregnated MI-386 (impregnated with nano-sizedBaO particles), or a 50:50 mixture of MI-386 and micron-sized BaOparticles, or a mixture of MI-386 impregnated with nano-sized BaOparticles and admixed with micron-sized BaO particles, may be used forthis component of the washcoat. In some embodiments, the alumina cancomprise from 5% to 30% nano-BaO-impregnated alumina and from 70% to 95%non-BaO-impregnated alumina. In some embodiments, the alumina cancomprise from 5% to 20% nano-BaO-impregnated alumina and from 80% to 95%non-BaO-impregnated alumina. In some embodiments, the alumina cancomprise from 8% to 16% nano-BaO-impregnated alumina and from 84% to 92%non-BaO-impregnated alumina. In one embodiment, 12%, or about 12%,nano-BaO-impregnated alumina is mixed with 88%, or about 88%, aluminawithout impregnated BaO. In one embodiment, 15%, or about 15%,nano-BaO-impregnated alumina is mixed with 85%, or about 85%, aluminawithout impregnated BaO.

In some embodiments, the alumina can comprise from 5% to 30%micron-sized BaO and from 70% to 95% non-BaO-impregnated alumina. Insome embodiments, the alumina can comprise from 5% to 20% micron-sizedBaO and from 80% to 95% non-BaO-impregnated alumina. In someembodiments, the alumina can comprise from 8% to 16% micron-sized-BaOand from 84% to 92% non-BaO-impregnated alumina. In one embodiment, 12%,or about 12%, micron-sized BaO is mixed with 88%, or about 88%, aluminawithout impregnated BaO. In one embodiment, 15%, or about 15%,micron-sized BaO is mixed with 85%, or about 85%, alumina withoutimpregnated BaO.

The ranges for the nano-sized BaO-alumina ratio, that is, the amount ofnano-BaO impregnated into the alumina, include 1-25% BaO to 75% to 99%aluminum oxide micron support; 3-20% BaO to 80% to 97% aluminum oxidemicron support; 5%-15% BaO to 85% to 95% aluminum oxide micron support;and about 15% BaO to about 85% aluminum oxide micron support, expressedas weight percentages. In one embodiment, the nano-BaO-impregnatedaluminum oxide comprises 15%, or about 15%, nano-BaO by weight and 85%,or about 85%, aluminum oxide by weight.

In some embodiments, the catalyst-containing washcoat composition orcatalyst-containing layer further comprises metal-oxide particles, suchas the metal oxide particles discussed above (e.g., porous metal-oxides,aluminum-oxides, porous aluminum-oxides, etc.). In some embodiments,these metal-oxide particles further comprise up to approximately 65%, upto approximately 60%, up to approximately 55%, or up to approximately54%, such as approximately 2% to approximately 54%, by weight of thecombination of the nano-on-nano-on-micron particles, the boehmiteparticles, the silica particles, and the metal-oxide particles in thecatalyst-containing washcoat composition or catalyst-containing layer.It is contemplated that the concentration ranges discussed above for thenano-on-nano-on-micron particles, the boehmite particles, and the silicaparticles can be applied to the combination of those materials with themetal-oxide particles.

In other embodiments, the catalyst-containing washcoat composition orcatalyst-containing layer comprises, consists essentially of, orconsists of zeolite particles, boehmite particles, andnano-on-nano-on-micron particles. In some embodiments, thenano-on-nano-on-micron particles make up between approximately 35% toapproximately 95% by weight of the combination of thenano-on-nano-on-micron particles, the boehmite particles, and thezeolite particles in the catalyst-containing washcoat composition orcatalyst-containing layer. In some embodiments, thenano-on-nano-on-micron particles make up between approximately 40% toapproximately 92% by weight of the combination of thenano-on-nano-on-micron particles, the boehmite particles, and thezeolite particles in the catalyst-containing washcoat composition orcatalyst-containing layer. In some embodiments, thenano-on-nano-on-micron particles make up between approximately 60% toapproximately 95% by weight of the combination of thenano-on-nano-on-micron particles, the boehmite particles, and thezeolite particles in the catalyst-containing washcoat composition orcatalyst-containing layer. In some embodiments, thenano-on-nano-on-micron particles make up between approximately 80% toapproximately 95% by weight of the combination of thenano-on-nano-on-micron particles, the boehmite particles, and thezeolite particles in the catalyst-containing washcoat composition orcatalyst-containing layer. In some embodiments, thenano-on-nano-on-micron particles make up between approximately 80% toapproximately 92% by weight of the combination of thenano-on-nano-on-micron particles, the boehmite particles, and thezeolite particles in the catalyst-containing washcoat composition orcatalyst-containing layer. In some embodiments, thenano-on-nano-on-micron particles make up approximately 92% by weight ofthe combination of the nano-on-nano-on-micron particles, the boehmiteparticles, and the zeolite particles in the catalyst-containing washcoatcomposition or catalyst-containing layer. In some embodiments, thezeolite particles make up less than approximately 20%, less thanapproximately 10%, or less than approximately 5%, by weight of thecombination of the nano-on-nano-on-micron particles, the boehmiteparticles, and the zeolite particles in the catalyst-containing washcoatcomposition or catalyst-containing layer. In some embodiments, thezeolite particles make up approximately 1% to approximately 5% byweight, such as about 5% by weight, of the combination of thenano-on-nano-on-micron particles, the boehmite particles, and thezeolite particles in the catalyst-containing washcoat composition orcatalyst-containing layer. In some embodiments, the boehmite particlesmake up approximately 2% to approximately 5% by weight of thecombination of the nano-on-nano-on-micron particles, the boehmiteparticles, and the zeolite particles in the catalyst-containing washcoatcomposition or catalyst-containing layer. In some embodiments, theboehmite particles make up approximately 3% by weight of the combinationof the nano-on-nano-on-micron particles, the boehmite particles, and thezeolite particles in the catalyst-containing washcoat composition orcatalyst-containing layer.

In some embodiments, the catalyst-containing washcoat composition orcatalyst-containing layer further includes metal-oxide particles, suchas the metal oxide particles discussed above (e.g., porous metal-oxides,aluminum-oxides, porous aluminum-oxides, etc.). In some embodiments,these metal-oxide particles make up approximately 0% to approximately54%, such as approximately 2% to approximately 54%, by weight of thecombination of the nano-on-nano-on-micron particles, the boehmiteparticles, the zeolite particles, and the metal-oxide particles in thecatalyst-containing washcoat composition or catalyst-containing layer.It is contemplated that the concentration ranges discussed above for thenano-on-nano-on-micron particles, the boehmite particles, and thezeolite particles can be applied to the combination of those materialswith the metal-oxide particles.

In some embodiments, the catalyst-containing washcoat compositions orcatalyst-containing layer further includes PNA material.

In some embodiments, the catalyst-containing washcoat composition ismixed with water and acid, such as acetic acid, prior to the coating ofthe substrate with the catalyst-containing washcoat composition, therebyforming an aqueous mixture of the catalyst-containing washcoatcomposition, water, and acid. This aqueous mixture of thecatalyst-containing washcoat composition, water, and acid is thenapplied to the substrate (where the substrate may or may not alreadyhave other washcoat layers applied to it). In some embodiments, the pHof this aqueous mixture is adjusted to a pH level of about 2 to about 7prior to it being applied to the substrate. In some embodiments, the pHof this aqueous mixture is adjusted to a pH level of about 4 prior to itbeing applied to the substrate. In some embodiments, the viscosity ofthe aqueous washcoat is adjusted by mixing with a cellulose solution,with corn starch, or with similar thickeners. In some embodiments, theviscosity is adjusted to a value between about 300 cP to about 1200 cP.

In some embodiments, the catalyst-containing washcoat compositioncomprises a thickness of approximately 50 g/l to approximately 250 g/l,such as approximately 50 g/l to approximately 140 g/l, approximately 70g/l to approximately 140 g/l, approximately 90 g/l to approximately 140g/l, or approximately 110 g/l to approximately 130 g/l. In someembodiments, the catalyst-containing washcoat composition comprises athickness of approximately 50 g/l, approximately 60 g/l, approximately70 g/l, approximately 80 g/l, approximately 90 g/l, approximately 100g/l, approximately 110 g/l, approximately 120 g/l, approximately 130g/l, or approximately 140 g/l. Preferably, the catalyst-containingwashcoat composition comprises a thickness of approximately 120 g/l.

PNA Material Washcoat Compositions and PNA Layers

PNA material may be used to store nitrogen oxide gases during the coldstart of an internal combustion engine. The PNA material can be appliedto a substrate of a catalytic converter as part of a washcoat. The PNAmaterial stores nitrogen oxide gases during low temperature engineoperation. In some embodiments, the PNA material in the PNA materialwashcoat can comprise PGM on support particles; alkali oxide or alkalineearth oxide on support particles; alkali oxide or alkaline earth oxideand PGM on support particles; a combination of alkali oxide or alkalineearth oxide on support particles and different alkali oxides or alkalineearth oxides each on different support particles in any ratio; acombination of alkali oxide or alkaline earth oxide on support particlesand PGM on support particles in any ratio; a combination of alkali oxideor alkaline earth oxide on support particles, different alkali oxides oralkaline earth oxides each on different support particles, and PGM onsupport particles in any ratio; a combination of alkali oxide oralkaline earth oxide and PGM on support particles and the same ordifferent alkali oxides or alkaline earth oxides each on differentsupport particles in any ratio; a combination of alkali oxide oralkaline earth oxide and PGM on support particles and PGM on supportparticles in any ratio; a combination of alkali oxide or alkaline earthoxide and PGM on support particles; the same or different alkali oxidesor alkaline earth oxides each on different support particles; and PGM onsupport particles in any ratio. In addition, various other combinationsof alkali oxides and alkaline earth oxides on support particles; PGM onsupport particles; and alkali oxides and alkaline earth oxides and PGMon support particles in any ratio can be employed, as discussed above.

In some embodiments, different PNA materials may not be mixed on asupport material. For example, if a combination of manganese oxide oncerium oxide support and magnesium oxide on cerium oxide support isused, the manganese oxide is impregnated onto cerium oxide supportmaterial and set aside. Separately, magnesium oxide is then impregnatedonto fresh cerium oxide support material. The manganese oxide/ceriumoxide and magnesium oxide/cerium oxide are then combined in the desiredratio of the PNA material.

Support particles can include, for example, bulk refractory oxides suchas alumina or cerium oxide. On example of cerium oxide includes HSA5,HSA20, or a mixture thereof from Rhodia. The cerium oxide particles maycontain zirconium oxide. The cerium oxide particles may containlanthanum and/or lanthanum oxide. In addition, the cerium oxideparticles may contain both zirconium oxide and lanthanum oxide. Thecerium oxide particles may also contain yttrium oxide. As such, thecerium oxide particles can include cerium oxide, cerium-zirconium oxide,cerium-lanthanum oxide, cerium-yttrium oxide, cerium-zirconium-lanthanumoxide, cerium-zirconium-yttrium oxide, cerium-lanthanum-yttrium oxide,cerium-zirconium-lanthanum-yttrium oxide particles, or a combinationthereof. In some embodiments, the nano-sized cerium oxide particlescontain 40-90 wt % cerium oxide, 5-60 wt % zirconium oxide, 1-15 wt %lanthanum oxide, and/or 1-10 wt % yttrium oxide. In one embodiment, thecerium oxide particles contain 86 wt % cerium oxide, 10 wt % zirconiumoxide, and 4 wt % lanthanum and/or lanthanum oxide. In anotherembodiment, the cerium oxide particles contain 40 wt % cerium oxide, 50wt % zirconium oxide, 5 wt % lanthanum oxide, and 5 wt % yttrium oxide.

Support particles can be micron-sized and/or nano-sized. Suitablemicron-sized support particles include micron-sized cerium oxideparticles including, but are not limited to, HSA5, HSA20, or a mixturethereof. In some embodiments, the support particles may include PGM inaddition to alkali oxide or alkaline earth oxide particles or mixturethereof. The PGM can include ruthenium, platinum, palladium, or amixture thereof. The alkali oxide or alkaline earth oxide particles canbe nano-sized or micron-sized, as described above. In some embodiments,PGM are added to the micron-sized support particles using wet chemistrytechniques. In some embodiments, PGM are added to the micron-sizedsupport particles using incipient wetness techniques. In someembodiments, PGM are added to nano-sized support particles usingincipient wetness and/or wet chemistry techniques. In some embodiments,PGM are added to support particles by plasma based methods describedabove to form composite PNA nanoparticles. In some embodiments, thesePNA composite nanoparticles are added to carrier particles to form NNmPNA particles or are embedded within carrier particles to form NNiM PNAparticles. As such, the PGM on support particles can include micro-PGMon micron support particles, nano-PGM on micron support particles, PNAnano-on-nano particles, PNA NNm particles, PNA NNiM particles, or PNAhybrid NNm/wet-chemistry particles described above. In some embodiments,the alkali oxide or alkaline earth oxide particles and PGM are on thesame micron-sized support particle. In other embodiments, the alkalioxide or alkaline earth oxide particles and PGM are on differentmicron-sized support particles.

In some embodiments, the PNA layer and washcoat compositions comprise,consist essentially of, or consist of PNA material and boehmiteparticles. Different configurations of the weight concentrations of thePNA material and boehmite particles may be employed. In the followingdescriptions, the percentages of the components of the washcoatcompositions are provided in terms of the amount of solids present inthe washcoat compositions, as the washcoat compositions can be providedin an aqueous suspension or, in some instances, as dry powder. The PNAlayer refers to the PNA washcoat composition after it has been appliedto the substrate, dried, and calcined.

In some embodiments, the PNA material comprises at least 50%, comprisemore than about 50%, or comprises about 50% to about 100% by weight ofthe combination of PNA material and boehmite particles in the PNAwashcoat composition or PNA material layer. In some embodiments, the PNAmaterial makes up approximately 60% to approximately 80%, for example,approximately 65% to approximately 70% or approximately 70% toapproximately 80%, by weight of the combination of PNA material andboehmite particles in the PNA material particle-containing washcoatcomposition or PNA material layer. In some embodiments, the PNA materialmakes up approximately 90% to approximately 100%, for example,approximately 90% to approximately 95% or approximately 95% toapproximately 100%, by weight of the combination of PNA material andboehmite particles in the PNA material particle-containing washcoatcomposition or PNA material layer. In some embodiments, the PNA materialmakes up approximately 95% to approximately 98% by weight of thecombination of PNA material and boehmite particles in the PNA materialparticle-containing washcoat composition or PNA material layer.

In some embodiments, the PNA material comprises cerium oxide. In someembodiments, cerium oxide (which may include zirconium oxide, lanthanum,lanthanum oxide, yttrium oxide or a combination thereof) makes upapproximately 57% to approximately 99% by weight of the combination ofPNA material and boehmite particles in the PNA washcoat composition orPNA material layer. In some embodiments, cerium oxide (which may includezirconium oxide, lanthanum, lanthanum oxide, yttrium oxide or acombination thereof) makes up approximately 59% to approximately 98% byweight of the combination of PNA material and boehmite particles in thePNA washcoat composition or PNA material layer. In some embodiments,cerium oxide (which may include zirconium oxide, lanthanum, lanthanumoxide, yttrium oxide or a combination thereof) makes up approximately85% to approximately 97% by weight of the combination of PNA materialand boehmite particles in the PNA washcoat composition or PNA materiallayer. In some embodiments, cerium oxide (which may include zirconiumoxide, lanthanum, lanthanum oxide, yttrium oxide or a combinationthereof) makes up approximately 85% to approximately 88% by weight ofthe combination of PNA material and boehmite particles in the PNAwashcoat composition or PNA material layer. In some embodiments, ceriumoxide (which may include zirconium oxide, lanthanum, lanthanum oxide,yttrium oxide or a combination thereof) makes up approximately 90% toapproximately 98% by weight of the combination of PNA material andboehmite particles in the PNA washcoat composition or PNA materiallayer. In some embodiments, cerium oxide (which may include zirconiumoxide, lanthanum, lanthanum oxide, yttrium oxide, or a combinationthereof) makes up approximately 93% to approximately 95% by weight ofthe combination of PNA material and boehmite particles in the PNAwashcoat composition or PNA material layer.

In some embodiments, the boehmite particles make up approximately 1% toapproximately 10% by weight of the combination of PNA material andboehmite particles in the PNA material-containing washcoat compositionor PNA material layer. In some embodiments, the boehmite particles makeup approximately 2% to approximately 5% by weight of the combination ofPNA material and boehmite particles in the PNA material-containingwashcoat composition or PNA material layer. In some embodiments, theboehmite particles make up approximately 3% by weight of the combinationof PNA material particles and boehmite particles in the PNAmaterial-containing washcoat composition or PNA material layer.

In one embodiment, palladium is used in an amount of from about 0.01% toabout 5% (by weight) of the amount of cerium oxide used in the PNAwashcoat composition or layer. (As described above, in all embodiments,the cerium oxide can include zirconium oxide, lanthanum, lanthanumoxide, yttrium oxide, or a combination thereof). In one embodiment,palladium is used in an amount of from about 0.5% to about 3% (byweight) of the amount of cerium oxide used in the PNA washcoatcomposition or layer. In one embodiment, palladium is used in an amountof from about 0.67% to about 2.67% (by weight) of the amount of ceriumoxide used in the PNA washcoat composition or layer. In anotherembodiment, the amount of cerium oxide used in the PNA washcoatcomposition or layer is from about 50 g/L to about 400 g/L. In anotherembodiment, the amount of cerium oxide used in the PNA washcoatcomposition or layer is from about 100 g/L to about 350 g/L. In anotherembodiment, the amount of cerium oxide used in the PNA washcoatcomposition or layer is from about 150 g/L to about 300 g/L. In anotherembodiment, the amount of cerium oxide used in the PNA washcoatcomposition or layer is greater than or equal to about 150 g/L. Inanother embodiment, Pd is used in an amount of from about 1.5% to about2.5% (by weight) of the amount of cerium oxide used in the PNA washcoatcomposition or layer, and the amount of cerium oxide used is from about100 g/L to about 200 g/L. In another embodiment, Pd is used in an amountof from about 0.5% to about 1.5% (by weight) of the amount of ceriumoxide used in the PNA washcoat composition or layer, and the amount ofcerium oxide used is from about 250 g/L to about 350 g/L. In anotherembodiment, Pd is used in an amount of from about 1% to about 2% (byweight) of the amount of cerium oxide used in the PNA washcoatcomposition or layer, and the amount of cerium oxide used is greaterthan or equal to about 150 g/L. In another embodiment, Pd is used in anamount of about 2% (by weight) of the amount of cerium oxide used in thePNA washcoat composition or layer, and the amount of cerium oxide usedis greater than or equal to about 150 g/L. In another embodiment, Pd isused in an amount of about 1% (by weight) of the amount of cerium oxideused in the PNA washcoat composition or layer, and the amount of ceriumoxide used is greater than or equal to about 300 g/L. In anotherembodiment, Pd is used in an amount of about 1 g/L to about 5 g/L. Inanother embodiment, Pd is used in an amount of about 2 g/L to about 4g/L. In another embodiment, Pd is used in an amount of about 3 g/L. Inanother embodiment, Pd is used in an amount of about 1 g/L to about 5g/L, and the amount of cerium oxide used in the PNA washcoat compositionor layer is from about 100 g/L to about 350 g/L. In another embodiment,Pd is used in an amount of about 2 g/L to about 4 g/L, and the amount ofcerium oxide used in the PNA washcoat composition or layer is from about100 g/L to about 350 g/L. In another embodiment, Pd is used in an amountof about 3 g/L, and the amount of cerium oxide used in the PNA washcoatcomposition or layer is from about 150 g/L to about 300 g/L. In anotherembodiment, Pd is used in an amount of about 1 g/L to about 5 g/L, andthe amount of cerium oxide used in the PNA washcoat composition or layeris from greater than or equal to about 150 g/L. In another embodiment,Pd is used in an amount of about 2 g/L to about 4 g/L, and the amount ofcerium oxide used in the PNA washcoat composition or layer is fromgreater than or equal to about 150 g/L. In another embodiment, Pd isused in an amount of about 3 g/L, and the amount of cerium oxide used inthe PNA washcoat composition or layer is from greater than or equal toabout 150 g/L. The PNA washcoat composition or layer can include Pd inlarger (cooler) engine systems (e.g., greater than 2.5 Liters).

In one embodiment, ruthenium is used in an amount of from about 0.01% toabout 15% (by weight) of the amount of cerium oxide used in the PNAwashcoat composition or layer. (As described above, in all embodiments,the cerium oxide can include zirconium oxide, lanthanum, lanthanumoxide, yttrium oxide, or a combination thereof). In one embodiment,ruthenium is used in an amount of from about 0.5% to about 12% (byweight) of the amount of cerium oxide used in the PNA washcoatcomposition or layer. In one embodiment, ruthenium is used in an amountof from about 1% to about 10% (by weight) of the amount of cerium oxideused in the PNA washcoat composition or layer. In another embodiment,the amount of cerium oxide used in the PNA washcoat composition or layeris from about 50 g/L to about 400 g/L. In another embodiment, the amountof cerium oxide used in the PNA washcoat composition or layer is fromabout 100 g/L to about 350 g/L. In another embodiment, the amount ofcerium oxide used in the PNA washcoat composition or layer is from about150 g/L to about 300 g/L. In another embodiment, the amount of ceriumoxide used in the PNA washcoat composition or layer is greater than orequal to about 150 g/L. In another embodiment, the amount of ceriumoxide used in the PNA washcoat composition or layer is greater than orequal to about 300 g/L. In another embodiment, Ru is used in an amountof from about 3% to about 4.5% (by weight) of the amount of cerium oxideused in the PNA washcoat composition or layer, and the amount of ceriumoxide used is from about 100 g/L to about 200 g/L. In anotherembodiment, Ru is used in an amount of from about 1% to about 2.5% (byweight) of the amount of cerium oxide used in the PNA washcoatcomposition or layer, and the amount of cerium oxide used is from about250 g/L to about 350 g/L. In another embodiment, Ru is used in an amountof from about 1.67% to about 4% (by weight) of the amount of ceriumoxide used in the PNA washcoat composition or layer, and the amount ofcerium oxide used is greater than or equal to about 150 g/L. In anotherembodiment, Ru is used in an amount of from about 1.67% to about 4% (byweight) of the amount of cerium oxide used in the PNA washcoatcomposition or layer, and the amount of cerium oxide used is greaterthan or equal to about 300 g/L. In another embodiment, Ru is used in anamount of about 3.33% to about 4% (by weight) of the amount of ceriumoxide used in the PNA washcoat composition or layer, and the amount ofcerium oxide used is greater than or equal to about 150 g/L. In anotherembodiment, Ru is used in an amount of about 1.67% to about 2% (byweight) of the amount of cerium oxide used in the PNA washcoatcomposition or layer, and the amount of cerium oxide used is greaterthan or equal to about 300 g/L. In another embodiment, Ru is used in anamount of about 1 g/L to about 20 g/L. In another embodiment, Ru is usedin an amount of about 3 g/L to about 15 g/L. In another embodiment, Ruis used in an amount of about 4 g/L to about 8 g/L. In anotherembodiment, Ru is used in an amount of about 5 g/L to about 6 g/L. Inanother embodiment, Ru is used in an amount of about 1 g/L to about 20g/L, and the amount of cerium oxide used in the PNA washcoat compositionor layer is from about 100 g/L to about 350 g/L. In another embodiment,Ru is used in an amount of about 3 g/L to about 15 g/L, and the amountof cerium oxide used in the PNA washcoat composition or layer is fromabout 100 g/L to about 350 g/L. In another embodiment, Ru is used in anamount of about 4 g/L to about 8 g/L, and the amount of cerium oxideused in the PNA washcoat composition or layer is from about 100 g/L toabout 350 g/L. In another embodiment, Ru is used in an amount of about 5g/L to about 6 g/L, and the amount of cerium oxide used in the PNAwashcoat composition or layer is from about 150 g/L to about 350 g/L. Inanother embodiment, Ru is used in an amount of about 1 g/L to about 20g/L, and the amount of cerium oxide used in the PNA washcoat compositionor layer is from greater than or equal to about 150 g/L. In anotherembodiment, Ru is used in an amount of about 3 g/L to about 15 g/L, andthe amount of cerium oxide used in the PNA washcoat composition or layeris from greater than or equal to about 150 g/L. In another embodiment,Ru is used in an amount of about 4 g/L to about 8 g/L, and the amount ofcerium oxide used in the PNA washcoat composition or layer is fromgreater than or equal to about 150 g/L. In another embodiment, Ru isused in an amount of about 5 g/L to about 6 g/L, and the amount ofcerium oxide used in the PNA washcoat composition or layer is fromgreater than or equal to about 150 g/L. In another embodiment, Ru isused in an amount of about 1 g/L to about 20 g/L, and the amount ofcerium oxide used in the PNA washcoat composition or layer is fromgreater than or equal to about 300 g/L. In another embodiment, Ru isused in an amount of about 3 g/L to about 15 g/L, and the amount ofcerium oxide used in the PNA washcoat composition or layer is fromgreater than or equal to about 300 g/L. In another embodiment, Ru isused in an amount of about 4 g/L to about 8 g/L, and the amount ofcerium oxide used in the PNA washcoat composition or layer is fromgreater than or equal to about 300 g/L. In another embodiment, Ru isused in an amount of about 5 g/L to about 6 g/L, and the amount ofcerium oxide used in the PNA washcoat composition or layer is fromgreater than or equal to about 300 g/L. The PNA washcoat composition orlayer can include Ru in small (hotter) engine systems (e.g., less than 2Liters).

In one embodiment, MgO is used in an amount of from about 1% to about20% (by weight) of the amount of the cerium oxide used in the washcoator layer. In one embodiment, MgO is used in an amount of from about 1%to about 15% (by weight) of the amount of the cerium oxide used in thewashcoat or layer. In one embodiment, MgO is used in an amount of fromabout 1% to about 10% (by weight) of the amount of the cerium oxide usedin the washcoat or layer. In another embodiment, the amount of ceriumoxide used in the washcoat or layer is from about 50 g/L to about 450g/L. In another embodiment, the amount of cerium oxide used in thewashcoat or layer is from about 100 g/L to about 400 g/L. In anotherembodiment, the amount of cerium oxide used in the washcoat or layer isfrom about 150 g/L to about 350 g/L. In another embodiment, MgO is usedin an amount of from about 2% to about 8% (by weight) of the amount ofthe cerium oxide used in the washcoat or layer, and the amount of ceriumoxide used is from about 150 g/L to about 350 g/L. In anotherembodiment, MgO is used in an amount of from about 2% to about 4% (byweight) of the amount of the cerium oxide used in the washcoat or layer,and the amount of cerium oxide used is from about 250 g/L to about 350g/L. In another embodiment, MgO is used in an amount of from about 6% toabout 8% (by weight) of the amount of the cerium oxide used in thewashcoat or layer, and the amount of cerium oxide used is from about 150g/L to about 250 g/L. In another embodiment, MgO is used in an amount ofabout 3% (by weight) of the amount of the cerium oxide used in thewashcoat or layer, and the amount of cerium oxide used is about 350 g/L.In another embodiment, MgO is used in an amount of about 7% (by weight)of the amount of the cerium oxide used in the washcoat or layer, and theamount of cerium oxide used is about 150 g/L. In another embodiment, MgOis used in an amount of about 10.5 g/L, and the amount of cerium oxideused in the washcoat or layer is from about 150 g/L to about 350 g/L.

In one embodiment, Mn₃O₄ is used in an amount of from about 1% to about30% (by weight) of the amount of the cerium oxide used in the washcoator layer. In one embodiment, Mn₃O₄ is used in an amount of from about 1%to about 25% (by weight) of the amount of the cerium oxide used in thewashcoat or layer. In one embodiment, Mn₃O₄ is used in an amount of fromabout 1% to about 20% (by weight) of the amount of the cerium oxide usedin the washcoat or layer. In another embodiment, the amount of ceriumoxide used in the washcoat or layer is from about 50 g/L to about 450g/L. In another embodiment, the amount of cerium oxide used in thewashcoat or layer is from about 100 g/L to about 400 g/L. In anotherembodiment, the amount of cerium oxide used in the washcoat or layer isfrom about 150 g/L to about 350 g/L. In another embodiment, Mn₃O₄ isused in an amount of from about 5% to about 20% (by weight) of theamount of the cerium oxide used in the washcoat or layer, and the amountof cerium oxide used is from about 150 g/L to about 350 g/L. In anotherembodiment, Mn₃O₄ is used in an amount of from about 5% to about 10% (byweight) of the amount of the cerium oxide used in the washcoat or layer,and the amount of cerium oxide used is from about 250 g/L to about 350g/L. In another embodiment, Mn₃O₄ is used in an amount of from about 15%to about 20% (by weight) of the amount of the cerium oxide used in thewashcoat or layer, and the amount of cerium oxide used is from about 150g/L to about 250 g/L. In another embodiment, Mn₃O₄ is used in an amountof about 8% (by weight) of the amount of the cerium oxide used in thewashcoat or layer, and the amount of cerium oxide used is about 350 g/L.In another embodiment, Mn₃O₄ is used in an amount of about 18.67% (byweight) of the amount of the cerium oxide used in the washcoat or layer,and the amount of cerium oxide used is about 150 g/L. In anotherembodiment, Mn₃O₄ is used in an amount of about 28 g/L, and the amountof cerium oxide used in the washcoat or layer is from about 150 g/L toabout 350 g/L.

In one embodiment, calcium oxide is used in an amount of from about 1%to about 20% (by weight) of the amount of the cerium oxide used in thewashcoat or layer. In one embodiment, calcium oxide is used in an amountof from about 1% to about 15% (by weight) of the amount of the ceriumoxide used in the washcoat or layer. In one embodiment, calcium oxide isused in an amount of from about 1% to about 10% (by weight) of theamount of the cerium oxide used in the washcoat or layer. In anotherembodiment, the amount of cerium oxide used in the washcoat or layer isfrom about 50 g/L to about 450 g/L. In another embodiment, the amount ofcerium oxide used in the washcoat or layer is from about 100 g/L toabout 400 g/L. In another embodiment, the amount of cerium oxide used inthe washcoat or layer is from about 150 g/L to about 350 g/L. In anotherembodiment, calcium oxide is used in an amount of from about 2% to about8% (by weight) of the amount of the cerium oxide used in the washcoat orlayer, and the amount of cerium oxide used is from about 150 g/L toabout 350 g/L. In another embodiment, calcium oxide is used in an amountof from about 2% to about 4% (by weight) of the amount of the ceriumoxide used in the washcoat or layer, and the amount of cerium oxide usedin the washcoat or layer is from about 250 g/L to about 350 g/L. Inanother embodiment, calcium oxide is used in an amount of from about 6%to about 8% (by weight) of the amount of the cerium oxide used in thewashcoat or layer, and the amount of cerium oxide used is from about 150g/L to about 250 g/L. In another embodiment, calcium oxide is used in anamount of about 3% (by weight) of the amount of the cerium oxide used inthe washcoat or layer, and the amount of cerium oxide used is about 350g/L. In another embodiment, calcium oxide is used in an amount of about7% (by weight) of the amount of the cerium oxide used in the washcoat orlayer, and the amount of cerium oxide used is about 150 g/L. In anotherembodiment, calcium oxide is used in an amount of about 10.5 g/L, andthe amount of cerium oxide used in the washcoat or layer is from about150 g/L to about 350 g/L.

In one embodiment, MgO is used in an amount of about 10.5 g/L, Mn₃O₄ isused in an amount of about 28 g/L, calcium oxide is used in an amount ofabout 10.5 g/L, and the amount of cerium oxide used in the washcoat orlayer is from about 150 g/L to about 350 g/L.

In one embodiment, MgO is used in an amount of about 10.5 g/L, Mn₃O₄ isused in an amount of about 28 g/L, calcium oxide is used in an amount ofabout 10.5 g/L, and the amount of cerium oxide used in the washcoat orlayer is from about 150 g/L to about 350 g/L.

In some embodiments, the PNA material-containing washcoat composition orPNA material does not comprise any platinum group metals. As discussedabove, the six platinum group metals are ruthenium, rhodium, palladium,osmium, iridium, and platinum. (PGM is often referred to catalystmetals). In some embodiments, the PNA material-containing washcoatcomposition or PNA material is characterized by a substantial absence ofany platinum group metals. In some embodiments, the PNAmaterial-containing washcoat composition or PNA material layer is 100%free of any platinum group metals. In some embodiments, the PNA materialcontaining washcoat composition or PNA material layer is approximately100% free of any platinum group metals. In some embodiments, the PNAmaterial-containing washcoat composition or PNA material layer does notcomprise any catalytic particles. In some embodiments, the PNA materialparticle-containing washcoat composition or PNA material layer ischaracterized by a substantial absence of any catalytic particles. Insome embodiments, the PNA material particle-containing washcoatcomposition or PNA material layer is 100% free of any catalyticparticles. In some embodiments, the PNA material particle-containingwashcoat composition or PNA material layer is approximately 100% free ofany catalytic particles.

As discussed above, in other embodiments, the PNA material washcoat maycontain PGM. In some embodiments, the PNA material is loaded with about1 g/L to about 20 g/L of PGM. In another embodiment, the PNA material isloaded with about 1 g/L to about 15 g/L of PGM. In another embodiment,the PNA material is loaded with about 6.0 g/L and less of PGM. Inanother embodiment, the PNA material is loaded with about 5.0 g/L andless of PGM. In another embodiment, the PNA material is loaded withabout 4.0 g/L and less of PGM. In another embodiment, the PNA materialis loaded with about 3.0 g/L and less of PGM. In another embodiment, thePNA material is loaded with about 2 g/L to about 4 g/L Pd. In anotherembodiment, the PNA material is loaded with about 3 g/L Pd. In anotherembodiment, the PNA material is loaded with about 3 g/L to about 15 g/LRu. In another embodiment, the PNA material is loaded with about 5 g/Lto about 6 g/L Ru.

PGM can be added to the support particles using wet chemistry techniquesdescribed above. PGM can also be added to the support particles usingincipient wetness techniques described above. PGM can be added tosupport particles using plasma based methods described above. In someembodiments, the PNA material washcoat includes support particlesimpregnated with alkali oxide or alkaline earth oxide particles andseparate PGM particles, including, for example, NNm or NNiM particles.In some embodiments, the micro-sized particles of the PGM NNm and NNiMparticles can be the micron-sized supports impregnated with alkali oxideor alkaline earth oxide particles. In some embodiments, the micro-sizedparticles of the PGM NNm can be impregnated with alkali oxide oralkaline earth oxide particles. In one embodiment, the NNm particles arenano-platinum group metals supported on nano-cerium oxide, wherein thenano-on-nano particles are supported on micron-sized cerium oxide. Inanother embodiment, the NNiM particles are nano-sized platinum groupmetals supported on nano-sized cerium oxide. In some embodiments, theplatinum group metal is Pt, Pd, Ru, or a mixture thereof. In someembodiments, the alkali oxide or alkaline earth oxide particles and PGMare on the same support particle. In other embodiments, the alkali oxideor alkaline earth oxide particles and PGM are on different supportparticles. The support particles can also be aluminum oxide.

The composite nanoparticles for use as components of the PNA washcoat orlayer can be produced by plasma-based methods as described above.

In some embodiments, the support particles may contain a mixture of 2:1to 100:1 platinum to palladium. In some embodiments, the supportparticles may contain a mixture of 2:1 to 75:1 platinum to palladium. Insome embodiments, the support particles may contain a mixture of 2:1 to50:1 platinum to palladium. In some embodiments, the support particlesmay contain a mixture of 2:1 to 25:1 platinum to palladium. In someembodiments, the support particles may contain a mixture of 2:1 to 15:1platinum to palladium. In some embodiments, the support particles maycontain a mixture of 2:1 to 10:1 platinum to palladium. In someembodiments, the support particles may contain a mixture of 2:1 platinumto palladium, or approximately 2:1 platinum to palladium. In someembodiments, the support particles may contain a mixture of 2:1 to 20:1platinum to palladium. In some embodiments, the support particles maycontain a mixture of 5:1 to 15:1 platinum to palladium. In someembodiments, the support particles may contain a mixture of 8:1 to 12:1platinum to palladium. In some embodiments, the support particles maycontain a mixture of 10:1 platinum to palladium, or approximately 10:1platinum to palladium. In some embodiments, the support particles maycontain a mixture of 2:1 to 8:1 platinum to palladium. In someembodiments, the support particles may contain a mixture of 3:1 to 5:1platinum to palladium. In some embodiments, the support particles maycontain a mixture of 4:1 platinum to palladium, or approximately 4:1platinum to palladium.

In some embodiments, the PNA material-containing washcoat composition orPNA material layer may include zeolites.

In some embodiments, the PNA material-containing washcoat composition ismixed with water and acid, such as acetic acid, prior to coating of asubstrate with the PNA material-containing washcoat composition, therebyforming an aqueous mixture of the PNA material-containing washcoatcomposition, water, and acid. This aqueous mixture of the PNAmaterial-containing washcoat composition, water, and acid may then beapplied to the substrate (where the substrate may or may not alreadyhave other washcoat layers applied to it). In some embodiments, the pHof this aqueous mixture may be adjusted to a pH level of about 2 toabout 7 prior to it being applied to the substrate. In some embodiments,the pH of this aqueous mixture may be adjusted to a pH level of about 4prior to it being applied to the substrate.

The washcoat layers can include materials that are less active or inertto exhausts. Such materials can be incorporated as supports for thereactive catalysts or to provide surface area for the metals. In someembodiments, the catalyst-containing washcoat composition furtherincludes “spacer” or “filler” particles, where the spacer particles may,for example, be ceramic, metal oxide, or metallic particles. In someembodiments, the spacer particles may be boehmite.

PNA Material/Zeolite Washcoat Compositions and PNA/Zeolite Layers

The PNA material and zeolite particles can be applied to a substrate ofa catalytic converter as part of the same washcoat. Both the PNAmaterial and the zeolite particles can be used to trap hazardous gasesduring cold start of an internal combustion engine.

In some embodiments, the PNA material and the zeolite particles layer(P/Z layer) and washcoat compositions comprise, consist essentially of,or consist of PNA material, zeolite particles, boehmite particles, andmetal-oxide particles. The metal-oxide particles are preferably porous.The metal-oxide particles may be aluminum-oxide particles (e.g., MI-386from Grace Davison or the like) or cerium oxide particles. Thealuminum-oxide particles may be porous. Different configurations of theweight concentrations of the PNA material, zeolite particles, boehmiteparticles, and metal-oxide particles may be employed. In the followingdescriptions, the percentages of the components of the washcoatcompositions are provided in terms of the amount of solids present inthe washcoat compositions, as the washcoat compositions can be providedin an aqueous suspension or, in some instances, as dry powder. The P/Zlayer refers to the P/Z washcoat composition after it has been appliedto the substrate, dried, and calcined.

In some embodiments, the PNA material and zeolite particles comprise atleast 50%, comprise more than about 50%, or comprise about 50% to about100% by weight of the combination of PNA material, zeolite particles,boehmite particles, and metal-oxide particles in the P/Z washcoatcomposition or P/Z 1 layer. In some embodiments, the PNA material andzeolite particles make up approximately 60% to approximately 80%, forexample, approximately 65% to approximately 70% or approximately 70% toapproximately 80%, by weight of the combination of PNA material, zeoliteparticles, boehmite particles, and metal-oxide particles in theP/Z-containing washcoat composition or P/Z layer.

In some embodiments, the boehmite particles make up approximately 1% toapproximately 10% by weight of the combination of PNA material, zeoliteparticles, boehmite particles, and metal-oxide particles in theP/Z-containing washcoat composition or P/Z layer. In some embodiments,the boehmite particles make up approximately 2% to approximately 5% byweight of the combination of PNA material, zeolite particles, boehmiteparticles, and metal-oxide particles in the P/Z-containing washcoatcomposition or P/Z layer. In some embodiments, the boehmite particlesmake up approximately 3% by weight of the combination of PNA material,zeolite particles, boehmite particles, and metal-oxide particles in theP/Z-containing washcoat composition or P/Z layer.

In one embodiment, palladium is used in an amount of from about 0.01% toabout 5% (by weight) of the amount of cerium oxide used in the PNAwashcoat composition or layer. (As described above, in all embodiments,the cerium oxide can include zirconium oxide, lanthanum, lanthanumoxide, yttrium oxide, or a combination thereof). In one embodiment,palladium is used in an amount of from about 0.5% to about 3% (byweight) of the amount of cerium oxide used in the PNA washcoatcomposition or layer. In one embodiment, palladium is used in an amountof from about 0.67% to about 2.67% (by weight) of the amount of ceriumoxide used in the PNA washcoat composition or layer. In anotherembodiment, the amount of cerium oxide used in the PNA washcoatcomposition or layer is from about 50 g/L to about 400 g/L. In anotherembodiment, the amount of cerium oxide used in the PNA washcoatcomposition or layer is from about 100 g/L to about 350 g/L. In anotherembodiment, the amount of cerium oxide used in the PNA washcoatcomposition or layer is from about 150 g/L to about 300 g/L. In anotherembodiment, the amount of cerium oxide used in the PNA washcoatcomposition or layer is greater than or equal to about 150 g/L. Inanother embodiment, Pd is used in an amount of from about 1.5% to about2.5% (by weight) of the amount of cerium oxide used in the PNA washcoatcomposition or layer, and the amount of cerium oxide used is from about100 g/L to about 200 g/L. In another embodiment, Pd is used in an amountof from about 0.5% to about 1.5% (by weight) of the amount of ceriumoxide used in the PNA washcoat composition or layer, and the amount ofcerium oxide used is from about 250 g/L to about 350 g/L. In anotherembodiment, Pd is used in an amount of from about 1% to about 2% (byweight) of the amount of cerium oxide used in the PNA washcoatcomposition or layer, and the amount of cerium oxide used is greaterthan or equal to about 150 g/L. In another embodiment, Pd is used in anamount of about 2% (by weight) of the amount of cerium oxide used in thePNA washcoat composition or layer, and the amount of cerium oxide usedis greater than or equal to about 150 g/L. In another embodiment, Pd isused in an amount of about 1% (by weight) of the amount of cerium oxideused in the PNA washcoat composition or layer, and the amount of ceriumoxide used is greater than or equal to about 300 g/L. In anotherembodiment, Pd is used in an amount of about 1 g/L to about 5 g/L. Inanother embodiment, Pd is used in an amount of about 2 g/L to about 4g/L. In another embodiment, Pd is used in an amount of about 3 g/L. Inanother embodiment, Pd is used in an amount of about 1 g/L to about 5g/L, and the amount of cerium oxide used in the PNA washcoat compositionor layer is from about 100 g/L to about 350 g/L. In another embodiment,Pd is used in an amount of about 2 g/L to about 4 g/L, and the amount ofcerium oxide used in the PNA washcoat composition or layer is from about100 g/L to about 350 g/L. In another embodiment, Pd is used in an amountof about 3 g/L, and the amount of cerium oxide used in the PNA washcoatcomposition or layer is from about 150 g/L to about 300 g/L. In anotherembodiment, Pd is used in an amount of about 1 g/L to about 5 g/L, andthe amount of cerium oxide used in the PNA washcoat composition or layeris from greater than or equal to about 150 g/L. In another embodiment,Pd is used in an amount of about 2 g/L to about 4 g/L, and the amount ofcerium oxide used in the PNA washcoat composition or layer is fromgreater than or equal to about 150 g/L. In another embodiment, Pd isused in an amount of about 3 g/L, and the amount of cerium oxide used inthe PNA washcoat composition or layer is from greater than or equal toabout 150 g/L. The PNA washcoat composition or layer can include Pd inlarger (cooler) engine systems (e.g., greater than 2.5 Liters).

In one embodiment, ruthenium is used in an amount of from about 0.01% toabout 15% (by weight) of the amount of cerium oxide used in the PNAwashcoat composition or layer. (As described above, in all embodiments,the cerium oxide can include zirconium oxide, lanthanum, lanthanumoxide, yttrium oxide, or a combination thereof). In one embodiment,ruthenium is used in an amount of from about 0.5% to about 12% (byweight) of the amount of cerium oxide used in the PNA washcoatcomposition or layer. In one embodiment, ruthenium is used in an amountof from about 1% to about 10% (by weight) of the amount of cerium oxideused in the PNA washcoat composition or layer. In another embodiment,the amount of cerium oxide used in the PNA washcoat composition or layeris from about 50 g/L to about 400 g/L. In another embodiment, the amountof cerium oxide used in the PNA washcoat composition or layer is fromabout 100 g/L to about 350 g/L. In another embodiment, the amount ofcerium oxide used in the PNA washcoat composition or layer is from about150 g/L to about 300 g/L. In another embodiment, the amount of ceriumoxide used in the PNA washcoat composition or layer is greater than orequal to about 150 g/L. In another embodiment, the amount of ceriumoxide used in the PNA washcoat composition or layer is greater than orequal to about 300 g/L. In another embodiment, Ru is used in an amountof from about 3% to about 4.5% (by weight) of the amount of cerium oxideused in the PNA washcoat composition or layer, and the amount of ceriumoxide used is from about 100 g/L to about 200 g/L. In anotherembodiment, Ru is used in an amount of from about 1% to about 2.5% (byweight) of the amount of cerium oxide used in the PNA washcoatcomposition or layer, and the amount of cerium oxide used is from about250 g/L to about 350 g/L. In another embodiment, Ru is used in an amountof from about 1.67% to about 4% (by weight) of the amount of ceriumoxide used in the PNA washcoat composition or layer, and the amount ofcerium oxide used is greater than or equal to about 150 g/L. In anotherembodiment, Ru is used in an amount of from about 1.67% to about 4% (byweight) of the amount of cerium oxide used in the PNA washcoatcomposition or layer, and the amount of cerium oxide used is greaterthan or equal to about 300 g/L. In another embodiment, Ru is used in anamount of about 3.33% to about 4% (by weight) of the amount of ceriumoxide used in the PNA washcoat composition or layer, and the amount ofcerium oxide used is greater than or equal to about 150 g/L. In anotherembodiment, Ru is used in an amount of about 1.67% to about 2% (byweight) of the amount of cerium oxide used in the PNA washcoatcomposition or layer, and the amount of cerium oxide used is greaterthan or equal to about 300 g/L. In another embodiment, Ru is used in anamount of about 1 g/L to about 20 g/L. In another embodiment, Ru is usedin an amount of about 3 g/L to about 15 g/L. In another embodiment, Ruis used in an amount of about 4 g/L to about 8 g/L. In anotherembodiment, Ru is used in an amount of about 5 g/L to about 6 g/L. Inanother embodiment, Ru is used in an amount of about 1 g/L to about 20g/L, and the amount of cerium oxide used in the PNA washcoat compositionor layer is from about 100 g/L to about 350 g/L. In another embodiment,Ru is used in an amount of about 3 g/L to about 15 g/L, and the amountof cerium oxide used in the PNA washcoat composition or layer is fromabout 100 g/L to about 350 g/L. In another embodiment, Ru is used in anamount of about 4 g/L to about 8 g/L, and the amount of cerium oxideused in the PNA washcoat composition or layer is from about 100 g/L toabout 350 g/L. In another embodiment, Ru is used in an amount of about 5g/L to about 6 g/L, and the amount of cerium oxide used in the PNAwashcoat composition or layer is from about 150 g/L to about 350 g/L. Inanother embodiment, Ru is used in an amount of about 1 g/L to about 20g/L, and the amount of cerium oxide used in the PNA washcoat compositionor layer is from greater than or equal to about 150 g/L. In anotherembodiment, Ru is used in an amount of about 3 g/L to about 15 g/L, andthe amount of cerium oxide used in the PNA washcoat composition or layeris from greater than or equal to about 150 g/L. In another embodiment,Ru is used in an amount of about 4 g/L to about 8 g/L, and the amount ofcerium oxide used in the PNA washcoat composition or layer is fromgreater than or equal to about 150 g/L. In another embodiment, Ru isused in an amount of about 5 g/L to about 6 g/L, and the amount ofcerium oxide used in the PNA washcoat composition or layer is fromgreater than or equal to about 150 g/L. In another embodiment, Ru isused in an amount of about 1 g/L to about 20 g/L, and the amount ofcerium oxide used in the PNA washcoat composition or layer is fromgreater than or equal to about 300 g/L. In another embodiment, Ru isused in an amount of about 3 g/L to about 15 g/L, and the amount ofcerium oxide used in the PNA washcoat composition or layer is fromgreater than or equal to about 300 g/L. In another embodiment, Ru isused in an amount of about 4 g/L to about 8 g/L, and the amount ofcerium oxide used in the PNA washcoat composition or layer is fromgreater than or equal to about 300 g/L. In another embodiment, Ru isused in an amount of about 5 g/L to about 6 g/L, and the amount ofcerium oxide used in the PNA washcoat composition or layer is fromgreater than or equal to about 300 g/L. The PNA washcoat composition orlayer can include Ru in small (hotter) engine systems (e.g., less than 2Liters).

In one embodiment, MgO is used in an amount of from about 1% to about20% (by weight) of the amount of the cerium oxide used in the washcoator layer. In one embodiment, MgO is used in an amount of from about 1%to about 15% (by weight) of the amount of the cerium oxide used in thewashcoat or layer. In one embodiment, MgO is used in an amount of fromabout 1% to about 10% (by weight) of the amount of the cerium oxide usedin the washcoat or layer. In another embodiment, the amount of ceriumoxide used in the washcoat or layer is from about 50 g/L to about 450g/L. In another embodiment, the amount of cerium oxide used in thewashcoat or layer is from about 100 g/L to about 400 g/L. In anotherembodiment, the amount of cerium oxide used in the washcoat or layer isfrom about 150 g/L to about 350 g/L. In another embodiment, MgO is usedin an amount of from about 2% to about 8% (by weight) of the amount ofthe cerium oxide used in the washcoat or layer, and the amount of ceriumoxide used is from about 150 g/L to about 350 g/L. In anotherembodiment, MgO is used in an amount of from about 2% to about 4% (byweight) of the amount of the cerium oxide used in the washcoat or layer,and the amount of cerium oxide used is from about 250 g/L to about 350g/L. In another embodiment, MgO is used in an amount of from about 6% toabout 8% (by weight) of the amount of the cerium oxide used in thewashcoat or layer, and the amount of cerium oxide used is from about 150g/L to about 250 g/L. In another embodiment, MgO is used in an amount ofabout 3% (by weight) of the amount of the cerium oxide used in thewashcoat or layer, and the amount of cerium oxide used is about 350 g/L.In another embodiment, MgO is used in an amount of about 7% (by weight)of the amount of the cerium oxide used in the washcoat or layer, and theamount of cerium oxide used is about 150 g/L. In another embodiment, MgOis used in an amount of about 10.5 g/L, and the amount of cerium oxideused in the washcoat or layer is from about 150 g/L to about 350 g/L.

In one embodiment, Mn₃O₄ is used in an amount of from about 1% to about30% (by weight) of the amount of the cerium oxide used in the washcoator layer. In one embodiment, Mn₃O₄ is used in an amount of from about 1%to about 25% (by weight) of the amount of the cerium oxide used in thewashcoat or layer. In one embodiment, Mn₃O₄ is used in an amount of fromabout 1% to about 20% (by weight) of the amount of the cerium oxide usedin the washcoat or layer. In another embodiment, the amount of ceriumoxide used in the washcoat or layer is from about 50 g/L to about 450g/L. In another embodiment, the amount of cerium oxide used in thewashcoat or layer is from about 100 g/L to about 400 g/L. In anotherembodiment, the amount of cerium oxide used in the washcoat or layer isfrom about 150 g/L to about 350 g/L. In another embodiment, Mn₃O₄ isused in an amount of from about 5% to about 20% (by weight) of theamount of the cerium oxide used in the washcoat or layer, and the amountof cerium oxide used is from about 150 g/L to about 350 g/L. In anotherembodiment, Mn₃O₄ is used in an amount of from about 5% to about 10% (byweight) of the amount of the cerium oxide used in the washcoat or layer,and the amount of cerium oxide used is from about 250 g/L to about 350g/L. In another embodiment, Mn₃O₄ is used in an amount of from about 15%to about 20% (by weight) of the amount of the cerium oxide used in thewashcoat or layer, and the amount of cerium oxide used is from about 150g/L to about 250 g/L. In another embodiment, Mn₃O₄ is used in an amountof about 8% (by weight) of the amount of the cerium oxide used in thewashcoat or layer, and the amount of cerium oxide used is about 350 g/L.In another embodiment, Mn₃O₄ is used in an amount of about 18.67% (byweight) of the amount of the cerium oxide used in the washcoat or layer,and the amount of cerium oxide used is about 150 g/L. In anotherembodiment, Mn₃O₄ is used in an amount of about 28 g/L, and the amountof cerium oxide used in the washcoat or layer is from about 150 g/L toabout 350 g/L.

In one embodiment, calcium oxide is used in an amount of from about 1%to about 20% (by weight) of the amount of the cerium oxide used in thewashcoat or layer. In one embodiment, calcium oxide is used in an amountof from about 1% to about 15% (by weight) of the amount of the ceriumoxide used in the washcoat or layer. In one embodiment, calcium oxide isused in an amount of from about 1% to about 10% (by weight) of theamount of the cerium oxide used in the washcoat or layer. In anotherembodiment, the amount of cerium oxide used in the washcoat or layer isfrom about 50 g/L to about 450 g/L. In another embodiment, the amount ofcerium oxide used in the washcoat or layer is from about 100 g/L toabout 400 g/L. In another embodiment, the amount of cerium oxide used inthe washcoat or layer is from about 150 g/L to about 350 g/L. In anotherembodiment, calcium oxide is used in an amount of from about 2% to about8% (by weight) of the amount of the cerium oxide used in the washcoat orlayer, and the amount of cerium oxide used is from about 150 g/L toabout 350 g/L. In another embodiment, calcium oxide is used in an amountof from about 2% to about 4% (by weight) of the amount of the ceriumoxide used in the washcoat or layer, and the amount of cerium oxide usedin the washcoat or layer is from about 250 g/L to about 350 g/L. Inanother embodiment, calcium oxide is used in an amount of from about 6%to about 8% (by weight) of the amount of the cerium oxide used in thewashcoat or layer, and the amount of cerium oxide used is from about 150g/L to about 250 g/L. In another embodiment, calcium oxide is used in anamount of about 3% (by weight) of the amount of the cerium oxide used inthe washcoat or layer, and the amount of cerium oxide used is about 350g/L. In another embodiment, calcium oxide is used in an amount of about7% (by weight) of the amount of the cerium oxide used in the washcoat orlayer, and the amount of cerium oxide used is about 150 g/L. In anotherembodiment, calcium oxide is used in an amount of about 10.5 g/L, andthe amount of cerium oxide used in the washcoat or layer is from about150 g/L to about 350 g/L.

In one embodiment, MgO is used in an amount of about 10.5 g/L, Mn₃O₄ isused in an amount of about 28 g/L, calcium oxide is used in an amount ofabout 10.5 g/L, and the amount of cerium oxide used in the washcoat orlayer is from about 150 g/L to about 350 g/L.

In some embodiments, the metal-oxide particles make up approximately 15%to approximately 38%, for example, approximately 15% to approximately30%, approximately 17% to approximately 23% or approximately 17% toapproximately 22%, by weight of the mixture of PNA material particles,zeolite particles, metal-oxide particles, and boehmite particles in theP/Z-containing washcoat composition or P/Z layer. In some embodiments,the metal-oxide particles make up approximately 15% to approximately 23%by weight of the mixture of PNA material, zeolite particles, metal-oxideparticles, and boehmite particles in the P/Z-containing washcoatcomposition or P/Z layer. In some embodiments, the metal-oxide particlesmake up approximately 25% to approximately 35% by weight of the mixtureof PNA material, zeolite particles, metal-oxide particles, and boehmiteparticles in the P/Z-containing washcoat composition or P/Z layer. Insome embodiments, the P/Z containing washcoat composition or P/Z layercontains about 3% boehmite particles, about 67% PNA material and zeoliteparticles, and about 30% porous aluminum-oxide particles.

In some embodiments, the P/Z-containing washcoat composition or P/Z doesnot comprise any platinum group metals. As discussed above, the sixplatinum group metals are ruthenium, rhodium, palladium, osmium,iridium, and platinum. In some embodiments, the P/Z containing washcoatcomposition or P/Z is characterized by a substantial absence of anyplatinum group metals. In some embodiments, the P/Z-containing washcoatcomposition or P/Z layer is 100% free of any platinum group metals. Insome embodiments, the P/Z containing washcoat composition or P/Z layeris approximately 100% free of any platinum group metals. In someembodiments, the P/Z-containing washcoat composition or P/Z layer doesnot comprise any catalytic particles. In some embodiments, the P/Zparticle-containing washcoat composition or P/Z layer is characterizedby a substantial absence of any catalytic particles. In someembodiments, the P/Z-containing washcoat composition or P P/Z layer is100% free of any catalytic particles. In some embodiments, the P/Zcontaining washcoat composition or P/Z layer is approximately 100% freeof any catalytic particles.

In other embodiments, the P/Z washcoat may comprise PGM. In someembodiments, the PNA material is loaded with about 1 g/L to about 20 g/Lof PGM. In another embodiment, the PNA material is loaded with about 1g/L to about 15 g/L of PGM. In another embodiment, the PNA material isloaded with about 6.0 g/L and less of PGM. In another embodiment, thePNA material is loaded with about 5.0 g/L and less of PGM. In anotherembodiment, the PNA material is loaded with about 4.0 g/L and less ofPGM. In another embodiment, the PNA material is loaded with about 3.0g/L and less of PGM. In another embodiment, the PNA material is loadedwith about 2 g/L to about 4 g/L Pd. In another embodiment, the PNAmaterial is loaded with about 3 g/L Pd. In another embodiment, the PNAmaterial is loaded with about 3 g/L to about 15 g/L Ru. In anotherembodiment, the PNA material is loaded with about 5 g/L to about 6 g/LRu.

PGM can be added to the support particles using wet chemistry techniquesdescribed above. PGM can also be added to the support particles usingincipient wetness techniques described above. PGM can be added tosupport particles using plasma based methods described above. In someembodiments, the PNA material washcoat includes support particlesimpregnated with alkali oxide or alkaline earth oxide particles andseparate PGM particles, including, for example, NNm or NNiM particles.In some embodiments, the micro-sized particles of the PGM NNm and NNiMparticles can be the micron-sized supports impregnated with alkali oxideor alkaline earth oxide particles. In some embodiments, the micro-sizedparticles of the PGM NNm can be impregnated with alkali oxide oralkaline earth oxide particles. In one embodiment, the NNm particles arenano-platinum group metals supported on nano-cerium oxide, wherein thenano-on-nano particles are supported on micron-sized cerium oxide. Inanother embodiment, the NNiM particles are nano-sized platinum groupmetals supported on nano-sized cerium oxide. In some embodiments, theplatinum group metal is Pt, Pd, Ru, or a mixture thereof. In someembodiments, the alkali oxide or alkaline earth oxide particles and PGMare on the same support particle. In other embodiments, the alkali oxideor alkaline earth oxide particles and PGM are on different supportparticles. The support particles can also be aluminum oxide.

The composite nanoparticles for use as components of the P/Z washcoat orlayer can be produced by plasma-based methods as described above.

In some embodiments, the support particles may contain a mixture of 2:1to 100:1 platinum to palladium. In some embodiments, the supportparticles may contain a mixture of 2:1 to 75:1 platinum to palladium. Insome embodiments, the support particles may contain a mixture of 2:1 to50:1 platinum to palladium. In some embodiments, the support particlesmay contain a mixture of 2:1 to 25:1 platinum to palladium. In someembodiments, the support particles may contain a mixture of 2:1 to 15:1platinum to palladium. In some embodiments, the support particles maycontain a mixture of 2:1 to 10:1 platinum to palladium. In someembodiments, the support particles may contain a mixture of 2:1 platinumto palladium, or approximately 2:1 platinum to palladium. In someembodiments, the support particles may contain a mixture of 2:1 to 20:1platinum to palladium. In some embodiments, the support particles maycontain a mixture of 5:1 to 15:1 platinum to palladium. In someembodiments, the support particles may contain a mixture of 8:1 to 12:1platinum to palladium. In some embodiments, the support particles maycontain a mixture of 10:1 platinum to palladium, or approximately 10:1platinum to palladium. In some embodiments, the support particles maycontain a mixture of 2:1 to 8:1 platinum to palladium. In someembodiments, the support particles may contain a mixture of 3:1 to 5:1platinum to palladium. In some embodiments, the support particles maycontain a mixture of 4:1 platinum to palladium, or approximately 4:1platinum to palladium.

In some embodiments, the P/Z-containing washcoat composition or P/Zlayer may include by weight about 2% to about 5% boehmite particles,about 60% to about 80% PNA material and zeolite particles, and the restporous aluminum-oxide particles (i.e., about 15% to about 38%). In oneembodiment, the P/Z containing washcoat composition or P/Z layerincludes by weight about 2% to about 5% boehmite particles, about 75% toabout 80% PNA material and zeolite particles, and the rest porousaluminum-oxide particles (i.e., about 15% to about 23%). In anotherembodiments, the P/Z containing washcoat composition or P/Z 1 layerincludes by weight about 2% to about 5% boehmite particles, about 65% toabout 70% PNA material and zeolite particles, and the rest porousaluminum-oxide particles (i.e., about 25% to about 33%). In someembodiment, the P/Z containing washcoat composition or P/Z layercontains about 3% boehmite particles, about 67% PNA material and zeoliteparticles, and about 30% porous aluminum-oxide particles. In someembodiments, the P/Z containing washcoat composition or P/Z layer doesnot contain any catalytic material. In some embodiments, the P/Zcontaining washcoat composition or P/Z layer does not contain anyplatinum group metals.

In some embodiments, the P/Z containing washcoat composition is mixedwith water and acid, such as acetic acid, prior to coating of asubstrate with the P/Z containing washcoat composition, thereby formingan aqueous mixture of the P/Z containing washcoat composition, water,and acid. This aqueous mixture of the P/Z containing washcoatcomposition, water, and acid may then be applied to the substrate (wherethe substrate may or may not already have other washcoat layers appliedto it). In some embodiments, the pH of this aqueous mixture may beadjusted to a pH level of about 2 to about 7 prior to it being appliedto the substrate. In some embodiments, the pH of this aqueous mixturemay be adjusted to a pH level of about 4 prior to it being applied tothe substrate.

The washcoat layers can include materials that are less active or inertto exhausts. Such materials can be incorporated as supports for thereactive catalysts or to provide surface area for the metals. In someembodiments, the catalyst-containing washcoat composition furtherincludes “spacer” or “filler” particles, where the spacer particles may,for example, be ceramic, metal oxide, or metallic particles. In someembodiments, the spacer particles may be boehmite.

PNA Material/Zeolite/Catalytically Active Washcoat Compositions andPNA/Zeolite/Catalyst Layers

The PNA material, zeolite particles, and catalytically active materialcan be applied to a substrate of a catalytic converter as part of thesame washcoat, thereby eliminated the need for excess washcoats. Boththe PNA material and the zeolite particles can be used to trap hazardousgases during cold start of an internal combustion engine and thecatalytically active particles can reduce and oxidize the hazardousparticles when they are released from the zeolites and PNA material.

In some embodiments, the PNA material and the zeolite particles layer(P/Z layer) and washcoat compositions comprise, consist essentially of,or consist of PNA material, zeolite particles, boehmite particles,metal-oxide particles, silica particles, alumina/sealant particles withor without BaO, and NNm particles. The compositions of the zeoliteparticles, PNA material, and catalytically active particles can be anyof those described above.

Catalytic Converters and Methods of Producing Catalytic Converters

In some embodiments, the disclosure provides for catalytic converters,which can comprise any of the washcoat layers and washcoatconfigurations described herein. The catalytic converters are useful ina variety of applications, such as in diesel or gasoline vehicles, suchas in light-duty diesel or gasoline vehicles.

FIG. 1 illustrates a catalytic converter in accordance with someembodiments. Catalytically active material is included in a washcoatcomposition, which is coated onto a substrate to form a coatedsubstrate. The coated substrate 114 is enclosed within an insulatingmaterial 112, which in turn is enclosed within a metallic container 110(of, for example, stainless steel). A heat shield 108 and a gas sensor(for example, an oxygen sensor) 106 are depicted. The catalyticconverter may be affixed to the exhaust system of the vehicle throughflanges 104 and 118. The exhaust gas, which includes the raw emissionsof hydrocarbons, carbon monoxide, and nitrogen oxides, enters thecatalytic converter at 102. As the raw emissions pass through thecatalytic converter, they react with the catalytically active materialon the coated substrate, resulting in tailpipe emissions of water,carbon dioxide, and nitrogen exiting at 120. FIG. 1A is a magnified viewof a section of the coated substrate 114, which shows the honeycombstructure of the coated substrate. The coated substrates, as describedbelow, may be incorporated into a catalytic converter for use in avehicle emissions control system.

FIGS. 2 and 3 illustrate various methods of forming coated substratesfor use in a catalytic converter. Any of the catalyst-containingwashcoats, zeolite particle-containing washcoats, and PNAmaterial-containing washcoats disclosed herein can be used in theseillustrative methods. In addition, any of the corner-fill washcoatsdisclosed herein can be used in any of the illustrative methods. Inaddition, layers or washcoats can be added to or removed from thesubstrates in any order.

FIG. 2 is a flow chart illustrating a PNA system preparation method 200in accordance with embodiments of the present disclosure. The PNA systemincludes catalytically active particles, zeolites, and PNA material inseparate washcoat layers on a substrate.

The PNA system preparation method 200 can start from Step 202. At Step204, a catalyst is prepared. At Step 206, a first washcoat containingthe catalyst is prepared. At Step 208, zeolite particles are prepared.At Step 210, a second washcoat containing the zeolite is prepared. Atstep 212, support particles containing NO_(x) adsorbers are prepared. AtStep 214, a third washcoat containing the support particles containingNO_(x) adsorbers is prepared. At Step 216, either the first washcoat,the second, or the third washcoat is applied to a substrate. At Step218, the substrate is dried. Examples of such drying processes include,but are not limited to, a hot-drying process, or a flash drying process.At Step 220, the washcoat-covered substrate is calcined. It iscontemplated that the length and temperature of the calcination processcan vary depending on the characteristics of the components in aparticular embodiment. At Step 222, one of the remaining two washcoatsis applied on the substrate. At Step 224, the substrate is dried.Examples of such drying processes include, but are not limited to, ahot-drying process, or a flash drying process. At Step 226, thewashcoat-covered substrate is calcined. It is contemplated that thelength and temperature of the calcination process can vary depending onthe characteristics of the components in a particular embodiment. AtStep 228, the final remaining washcoat is applied on the substrate. AtStep 230, the substrate is dried. At Step 232, the washcoat-coveredsubstrate with catalytically active particles, zeolite particles, andsupport particles impregnated with NO_(x) storing materials contained inseparate layers is calcined. It is contemplated that the length andtemperature of the calcination process can vary depending on thecharacteristics of the components in a particular embodiment. The method200 ends at Step 234. The oxide-oxide bonds formed during thecalcination process firmly retain the nanoparticles, so that the chancesfor the nanoparticles to move at high temperature and to encounter andreact with each other are avoided.

The method 200 can be readily modified to apply additional washcoatlayers as desired, before or after any step illustrated. Preferably, adrying process and a calcining process are performed between eachcoating step.

FIG. 3 is a flow chart illustrating an PNA system preparation method 300in accordance with embodiments of the present disclosure. The PNA systemincludes catalytically active particles in a washcoat layer on asubstrate and zeolites and PNA material contained in a separate singlewashcoat layer.

The PNA system preparation method 300 can start from Step 302. At Step304, a catalyst is prepared. At Step 306, a first washcoat containingthe catalyst is prepared. At Step 308, zeolites are prepared. At step310, support particles containing NO_(x) adsorbers are prepared. At Step312, a second washcoat containing the zeolites and the support particlesfor NO_(x) adsorption/storage is prepared. At Step 314, either the firstwashcoat or the second washcoat is applied to a substrate. At Step 316,the substrate is dried. Examples of such drying processes include, butare not limited to, a hot-drying process, or a flash drying process. AtStep 318, the washcoat-covered substrate is calcined. It is contemplatedthat the length and temperature of the calcination process can varydepending on the characteristics of the components in a particularembodiment. At Step 320, the other washcoat is applied on the substrate.At Step 322, the substrate is dried. Examples of such drying processesinclude, but are not limited to, a hot-drying process, or a flash dryingprocess. At Step 324, the washcoat-covered substrate with catalyticallyactive particles, and zeolite particles and support particlesimpregnated with NO_(x) storing materials contained in the same layer,is calcined. It is contemplated that the length and temperature of thecalcination process can vary depending on the characteristics of thecomponents in a particular embodiment. The method 300 ends at Step 326.The oxide-oxide bonds formed during the calcination process firmlyretain the nanoparticles, so that the chances for the nanoparticles tomove at high temperature and to encounter and react with each other areavoided.

The method 300 can be readily modified to apply additional washcoatlayers as desired, before or after any step illustrated. Preferably, adrying process and a calcining process are performed between eachcoating step.

In addition, a PNA system can include catalytically active particles,zeolites, and PNA material contained in a single washcoat layer on asubstrate.

FIG. 4 shows a single rectangular channel 400 in a coated substratecoated in the S-F-C-P-Z configuration, without additional washcoatlayers. The wall 410 of the substrate channel has been coated withcorner-fill washcoat layer 420, then catalyst-containing washcoat layer430, then PNA material-containing washcoat layer 440, then zeoliteparticle-containing washcoat layer 450. Exhaust gases pass through thelumen 460 of the channel when the coated substrate is employed in acatalytic converter as part of an emissions control system.

Exhaust Systems, Vehicles, and Emissions Performance

Emission standards for unburned hydrocarbons, carbon monoxide andnitrogen oxide contaminants have been set by various governments andmust be met by older, as well as new, vehicles. In order to meet suchstandards, catalytic converters containing a PNA system are located inthe exhaust gas line of internal combustion engines. PNA systems firststore, then reduce, nitrogen oxides to nitrogen.

In some embodiments, a coated substrate as disclosed herein is housedwithin a catalytic converter in a position configured to receive exhaustgas from an internal combustion engine, such as in an exhaust system ofan internal combustion engine. The catalytic converter can be used withthe exhaust from a diesel or gasoline engine, such as a light-dutydiesel or gasoline engine. The catalytic converter can be installed on avehicle containing a diesel or gasoline engine, such as a light-dutydiesel or gasoline engine. The catalytic converter may even be installedon a vehicle containing a gasoline engine.

The coated substrate is placed into a housing, such as that shown inFIG. 1, which can in turn be placed into an exhaust system (alsoreferred to as an exhaust treatment system) of an internal combustionengine. The internal combustion engine can be a diesel or gasolineengine, such as a light-duty diesel or gasoline engine, such as theengine of a light-duty diesel or gasoline vehicle. The exhaust system ofthe internal combustion engine receives exhaust gases from the engine,typically into an exhaust manifold, and delivers the exhaust gases to anexhaust treatment system. The catalytic converter forms part of theexhaust system and is often referred to as the diesel oxidation catalyst(DOC). An example of a DOC can be found in U.S. patent application Ser.No. 13/589,024 (now U.S. Pat. No. 8,679,433), Ser. No. 14/340,351 (U.S.Patent Publ. No. 2015/0093312), and Ser. No. 14/521,295 (now U.S. Pat.No. 9,427,732) and U.S. Pat. No. 8,679,433, which are herebyincorporated by reference in its entirety. The exhaust system can alsoinclude a diesel particulate filter (DPF) and/or a selective catalyticreduction unit (SCR unit) and/or a lean NO_(x) trap (LNT); typicalarrangements, in the sequence that exhaust gases are received from theengine, are DOC-DPF and DOC-DPF-SCR or in an LNT system. The exhaustsystem can also include other components, such as oxygen sensors, HEGO(heated exhaust gas oxygen) sensors, UEGO (universal exhaust gas oxygen)sensors, sensors for other gases, and temperature sensors. The exhaustsystem can also include a controller such as an engine control unit(ECU), a microprocessor, or an engine management computer, which canadjust various parameters in the vehicle (fuel flow rate, fuel/airratio, fuel injection, engine timing, valve timing, etc.) in order tooptimize the components of the exhaust gases that reach the exhausttreatment system, so as to manage the emissions released into theenvironment.

“Treating” an exhaust gas, such as the exhaust gas from a gasoline ordiesel or gasoline engine, refers to having the exhaust gas proceedthrough an exhaust system (exhaust treatment system) prior to releaseinto the environment.

The United States Environmental Protection Agency defines a “light-dutydiesel vehicle” (“LDDV”) as a diesel-powered motor vehicle, other than adiesel bus, that has a gross vehicle weight rating of 8,500 pounds orless and is designed primarily for transporting persons or property. InEurope, a “light-duty diesel or gasoline engine” has been considered tobe an engine used in a vehicle of 3.5 metric tons or less (7,716 poundsor less) (see European directives 1992/21 EC and 1995/48 EC). In someembodiments, a light-duty diesel vehicle is a diesel vehicle weighingabout 8,500 pounds or less, or about 7,700 pounds or less, and alight-duty diesel engine is an engine used in a light-duty dieselvehicle.

When used in a catalytic converter, the coated substrates disclosedherein may provide a significant improvement over other catalyticconverters. The PNA material or the PNA material and the zeolites in thecoated substrate act as an intermediate storage device for the exhaustgases while the exhaust gas is still cold. The undesirable gases(including, but not limited to, hydrocarbons, carbon monoxide, andnitrogen oxides or NO_(x)) adsorb to the PNA material or the PNA andzeolites (NO_(x) adsorbs to the PNA material) during the cold startphase, while the catalyst is not yet active, and are released later whenthe catalyst reaches a temperature sufficient to effectively decomposethe gases (that is, the light-off temperature). The coated substrates,catalytic converters, and exhaust treatment systems described herein areuseful for any vehicle employing an LNT, SCR, or other NSC system.

In some embodiments, catalytic converters and exhaust treatment systemsemploying the coated substrates disclosed herein display emissions of3400 mg/mile or less of CO emissions and 400 mg/mile or less of NO_(x)emissions; 3400 mg/mile or less of CO emissions and 200 mg/mile or lessof NO_(x) emissions; or 1700 mg/mile or less of CO emissions and 200mg/mile or less of NO_(x) emissions. The disclosed coated substrates,used as catalytic converter substrates, can be used in an emissionsystem to meet or exceed these standards. In some embodiments, thecoated substrate is used in a catalytic converter (diesel oxidationcatalyst) in the configuration DOC-DPF or DOC-DPF-SCR or in an LNTsystem to meet or exceed these standards.

Emissions limits for Europe are summarized at the URLeuropa.eu/legislation_summaries/environment/air_pollution/128186_en.htm.The Euro 5 emissions standards, in force as of September 2009, specify alimit of 500 mg/km of CO emissions, 180 mg/km of NO_(x) emissions, and230 mg/km of HC (hydrocarbon)+NO_(x) emissions. The Euro 6 emissionsstandards, scheduled for implementation as of September 2014, specify alimit of 500 mg/km of CO emissions, 80 mg/km of NO_(x) emissions, and170 mg/km of HC (hydrocarbon)+NO_(x) emissions. The disclosed catalyticconverter substrates can be used in an emission system to meet or exceedthese standards. In some embodiments, the coated substrate is used in acatalytic converter (diesel oxidation catalyst) in the configurationDOC-DPF or DOC-DPF-SCR or in an LNT system to meet or exceed thesestandards.

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure, loaded with 4.0 g/L of PGM or less displays acarbon monoxide light-off temperature at least 5° C. lower than acatalytic converter made with wet chemistry methods and having the sameor similar PGM loading. In some embodiments, a catalytic converter madewith a coated substrate of the present disclosure, loaded with 4.0 g/Lof PGM or less, displays a carbon monoxide light-off temperature atleast 10° C. lower than a catalytic converter made with wet chemistrymethods and having the same or similar PGM loading. In some embodiments,a catalytic converter made with a coated substrate of the presentdisclosure, loaded with 4.0 g/L of PGM or less, displays a carbonmonoxide light-off temperature at least 15° C. lower than a catalyticconverter made with wet chemistry methods and having the same or similarPGM loading. In some embodiments, the catalytic converter made with acoated substrate of the present disclosure demonstrates any of theforegoing performance standards after about 50,000 km, about 50,000miles, about 75,000 km, about 75,000 miles, about 100,000 km, about100,000 miles, about 125,000 km, about 125,000 miles, about 150,000 km,or about 150,000 miles of operation (for both the catalytic convertermade with a coated substrate of the present disclosure and thecomparative catalytic converter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure, loaded with 4.0 g/L of PGM or less, displaysa hydrocarbon light-off temperature at least 5° C. lower than acatalytic converter made with wet chemistry methods and having the sameor similar PGM loading. In some embodiments, a catalytic converter madewith a coated substrate of the present disclosure, loaded with 4.0 g/Lof PGM or less, displays a hydrocarbon light-off temperature at least10° C. lower than a catalytic converter made with wet chemistry methodsand having the same or similar PGM loading. In some embodiments, acatalytic converter made with a coated substrate of the presentdisclosure, loaded with 4.0 g/L of PGM or less, displays a hydrocarbonlight-off temperature at least 15° C. lower than a catalytic convertermade with wet chemistry methods and having the same or similar PGMloading. In some embodiments, the catalytic converter made with a coatedsubstrate of the present disclosure demonstrates any of the foregoingperformance standards after about 50,000 km, about 50,000 miles, about75,000 km, about 75,000 miles, about 100,000 km, about 100,000 miles,about 125,000 km, about 125,000 miles, about 150,000 km, or about150,000 miles of operation (for both the catalytic converter made with acoated substrate of the present disclosure and the comparative catalyticconverter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure, loaded with 4.0 g/L of PGM or less, displaysa nitrogen oxide light-off temperature at least 5° C. lower than acatalytic converter made with wet chemistry methods and having the sameor similar PGM loading. In some embodiments, a catalytic converter madewith a coated substrate of the present disclosure, loaded with 4.0 g/Lof PGM or less, displays a nitrogen oxide light-off temperature at least10° C. lower than a catalytic converter made with wet chemistry methodsand having the same or similar PGM loading. In some embodiments, acatalytic converter made with a coated substrate of the presentdisclosure, loaded with 4.0 g/L of PGM or less, displays a nitrogenoxide light-off temperature at least 15° C. lower than a catalyticconverter made with wet chemistry methods and having the same or similarPGM loading. In some embodiments, the catalytic converter made with acoated substrate of the present disclosure demonstrates any of theforegoing performance standards after about 50,000 km, about 50,000miles, about 75,000 km, about 75,000 miles, about 100,000 km, about100,000 miles, about 125,000 km, about 125,000 miles, about 150,000 km,or about 150,000 miles of operation (for both the catalytic convertermade with a coated substrate of the present disclosure and thecomparative catalytic converter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure, loaded with 3.0 g/L of PGM or less, displaysa carbon monoxide light-off temperature at least 5° C. lower than acatalytic converter made with wet chemistry methods and having the sameor similar PGM loading. In some embodiments, a catalytic converter madewith a coated substrate of the present disclosure, loaded with 3.0 g/Lof PGM or less, displays a carbon monoxide light-off temperature atleast 10° C. lower than a catalytic converter made with wet chemistrymethods and having the same or similar PGM loading. In some embodiments,a catalytic converter made with a coated substrate of the presentdisclosure, loaded with 3.0 g/L of PGM or less, displays a carbonmonoxide light-off temperature at least 15° C. lower than a catalyticconverter made with wet chemistry methods and having the same or similarPGM loading. In some embodiments, the catalytic converter made with acoated substrate of the present disclosure demonstrates any of theforegoing performance standards after about 50,000 km, about 50,000miles, about 75,000 km, about 75,000 miles, about 100,000 km, about100,000 miles, about 125,000 km, about 125,000 miles, about 150,000 km,or about 150,000 miles of operation (for both the catalytic convertermade with a coated substrate of the present disclosure and thecomparative catalytic converter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure, loaded with 3.0 g/L of PGM or less, displaysa hydrocarbon light-off temperature at least 5° C. lower than acatalytic converter made with wet chemistry methods and having the sameor similar PGM loading. In some embodiments, a catalytic converter madewith a coated substrate of the present disclosure, loaded with 3.0 g/Lof PGM or less, displays a hydrocarbon light-off temperature at least10° C. lower than a catalytic converter made with wet chemistry methodsand having the same or similar PGM loading. In some embodiments, acatalytic converter made with a coated substrate of the presentdisclosure, loaded with 3.0 g/L of PGM or less, displays a hydrocarbonlight-off temperature at least 15° C. lower than a catalytic convertermade with wet chemistry methods and having the same or similar PGMloading. In some embodiments, the catalytic converter made with a coatedsubstrate of the present disclosure demonstrates any of the foregoingperformance standards after about 50,000 km, about 50,000 miles, about75,000 km, about 75,000 miles, about 100,000 km, about 100,000 miles,about 125,000 km, about 125,000 miles, about 150,000 km, or about150,000 miles of operation (for both the catalytic converter made with acoated substrate of the present disclosure and the comparative catalyticconverter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure, loaded with 3.0 g/L of PGM or less, displaysa nitrogen oxide light-off temperature at least 5° C. lower than acatalytic converter made with wet chemistry methods and having the sameor similar PGM loading. In some embodiments, a catalytic converter madewith a coated substrate of the present disclosure, loaded with 3.0 g/Lof PGM or less, displays a nitrogen oxide light-off temperature at least10° C. lower than a catalytic converter made with wet chemistry methodsand having the same or similar PGM loading. In some embodiments, acatalytic converter made with a coated substrate of the presentdisclosure, loaded with 3.0 g/L of PGM or less, displays a nitrogenoxide light-off temperature at least 15° C. lower than a catalyticconverter made with wet chemistry methods and having the same or similarPGM loading. In some embodiments, the catalytic converter made with acoated substrate of the present disclosure demonstrates any of theforegoing performance standards after about 50,000 km, about 50,000miles, about 75,000 km, about 75,000 miles, about 100,000 km, about100,000 miles, about 125,000 km, about 125,000 miles, about 150,000 km,or about 150,000 miles of operation (for both the catalytic convertermade with a coated substrate of the present disclosure and thecomparative catalytic converter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure, loaded with 2.0 g/L of PGM or less, displaysa carbon monoxide light-off temperature at least 5° C. lower than acatalytic converter made with wet chemistry methods and having the sameor similar PGM loading. In some embodiments, a catalytic converter madewith a coated substrate of the present disclosure, loaded with 2.0 g/Lof PGM or less, displays a carbon monoxide light-off temperature atleast 10° C. lower than a catalytic converter made with wet chemistrymethods and having the same or similar PGM loading. In some embodiments,a catalytic converter made with a coated substrate of the presentdisclosure, loaded with 2.0 g/L of PGM or less, displays a carbonmonoxide light-off temperature at least 15° C. lower than a catalyticconverter made with wet chemistry methods and having the same or similarPGM loading. In some embodiments, the catalytic converter made with acoated substrate of the present disclosure demonstrates any of theforegoing performance standards after about 50,000 km, about 50,000miles, about 75,000 km, about 75,000 miles, about 100,000 km, about100,000 miles, about 125,000 km, about 125,000 miles, about 150,000 km,or about 150,000 miles of operation (for both the catalytic convertermade with a coated substrate of the present disclosure and thecomparative catalytic converter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure, loaded with 2.0 g/L of PGM or less, displaysa hydrocarbon light-off temperature at least 5° C. lower than acatalytic converter made with wet chemistry methods and having the sameor similar PGM loading. In some embodiments, a catalytic converter madewith a coated substrate of the present disclosure, loaded with 2.0 g/Lof PGM or less, displays a hydrocarbon light-off temperature at least10° C. lower than a catalytic converter made with wet chemistry methodsand having the same or similar PGM loading. In some embodiments, acatalytic converter made with a coated substrate of the presentdisclosure, loaded with 2.0 g/L of PGM or less, displays a hydrocarbonlight-off temperature at least 15° C. lower than a catalytic convertermade with wet chemistry methods and having the same or similar PGMloading. In some embodiments, the catalytic converter made with a coatedsubstrate of the present disclosure demonstrates any of the foregoingperformance standards after about 50,000 km, about 50,000 miles, about75,000 km, about 75,000 miles, about 100,000 km, about 100,000 miles,about 125,000 km, about 125,000 miles, about 150,000 km, or about150,000 miles of operation (for both the catalytic converter made with acoated substrate of the present disclosure and the comparative catalyticconverter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure, loaded with 2.0 g/L of PGM or less, displaysa nitrogen oxide light-off temperature at least 5° C. lower than acatalytic converter made with wet chemistry methods and having the sameor similar PGM loading. In some embodiments, a catalytic converter madewith a coated substrate of the present disclosure, loaded with 2.0 g/Lof PGM or less, displays a nitrogen oxide light-off temperature at least10° C. lower than a catalytic converter made with wet chemistry methodsand having the same or similar PGM loading. In some embodiments, acatalytic converter made with a coated substrate of the presentdisclosure, loaded with 2.0 g/L of PGM or less, displays a nitrogenoxide light-off temperature at least 15° C. lower than a catalyticconverter made with wet chemistry methods and having the same or similarPGM loading. In some embodiments, the catalytic converter made with acoated substrate of the present disclosure demonstrates any of theforegoing performance standards after about 50,000 km, about 50,000miles, about 75,000 km, about 75,000 miles, about 100,000 km, about100,000 miles, about 125,000 km, about 125,000 miles, about 150,000 km,or about 150,000 miles of operation (for both the catalytic convertermade with a coated substrate of the present disclosure and thecomparative catalytic converter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure displays a carbon monoxide light-offtemperature within ±3° C. of the carbon monoxide light-off temperatureof a catalytic converter made with wet chemistry methods, while thecatalytic converter made with a coated substrate employing at leastabout 30% less, up to about 30% less, at least about 40% less, up toabout 40% less, at least about 50% less, or up to about 50% lesscatalyst than the catalytic converter made with wet chemistry methods.In some embodiments, the catalytic converter made with a coatedsubstrate of the present disclosure demonstrates this performance afterabout 50,000 km, about 50,000 miles, about 75,000 km, about 75,000miles, about 100,000 km, about 100,000 miles, about 125,000 km, about125,000 miles, about 150,000 km, or about 150,000 miles of operation(for both the catalytic converter made with a coated substrate of thepresent disclosure and the comparative catalytic converter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure displays a carbon monoxide light-offtemperature within ±2° C. of the carbon monoxide light-off temperatureof a catalytic converter made with wet chemistry methods, while thecatalytic converter made with a coated substrate employing at leastabout 30% less, up to about 30% less, at least about 40% less, up toabout 40% less, at least about 50% less, or up to about 50% lesscatalyst than the catalytic converter made with wet chemistry methods.In some embodiments, the catalytic converter made with a coatedsubstrate of the present disclosure demonstrates this performance afterabout 50,000 km, about 50,000 miles, about 75,000 km, about 75,000miles, about 100,000 km, about 100,000 miles, about 125,000 km, about125,000 miles, about 150,000 km, or about 150,000 miles of operation(for both the catalytic converter made with a coated substrate of thepresent disclosure and the comparative catalytic converter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure displays a carbon monoxide light-offtemperature within ±1° C. of the carbon monoxide light-off temperatureof a catalytic converter made with wet chemistry methods, while thecatalytic converter made with a coated substrate employing at leastabout 30% less, up to about 30% less, at least about 40% less, up toabout 40% less, at least about 50% less, or up to about 50% lesscatalyst than the catalytic converter made with wet chemistry methods.In some embodiments, the catalytic converter made with a coatedsubstrate of the present disclosure demonstrates this performance afterabout 50,000 km, about 50,000 miles, about 75,000 km, about 75,000miles, about 100,000 km, about 100,000 miles, about 125,000 km, about125,000 miles, about 150,000 km, or about 150,000 miles of operation(for both the catalytic converter made with a coated substrate of thepresent disclosure and the comparative catalytic converter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure displays a carbon monoxide light-offtemperature within ±3° C. of the hydrocarbon light-off temperature of acatalytic converter made with wet chemistry methods, while the catalyticconverter made with a coated substrate employing at least about 30%less, up to about 30% less, at least about 40% less, up to about 40%less, at least about 50% less, or up to about 50% less catalyst than thecatalytic converter made with wet chemistry methods. In someembodiments, the catalytic converter made with a coated substrate of thepresent disclosure demonstrates this performance after about 50,000 km,about 50,000 miles, about 75,000 km, about 75,000 miles, about 100,000km, about 100,000 miles, about 125,000 km, about 125,000 miles, about150,000 km, or about 150,000 miles of operation (for both the catalyticconverter made with a coated substrate of the present disclosure and thecomparative catalytic converter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure displays a carbon monoxide light-offtemperature within ±2° C. of the hydrocarbon light-off temperature of acatalytic converter made with wet chemistry methods, while the catalyticconverter made with a coated substrate employing at least about 30%less, up to about 30% less, at least about 40% less, up to about 40%less, at least about 50% less, or up to about 50% less catalyst than thecatalytic converter made with wet chemistry methods. In someembodiments, the catalytic converter made with a coated substrate of thepresent disclosure demonstrates this performance after about 50,000 km,about 50,000 miles, about 75,000 km, about 75,000 miles, about 100,000km, about 100,000 miles, about 125,000 km, about 125,000 miles, about150,000 km, or about 150,000 miles of operation (for both the catalyticconverter made with a coated substrate of the present disclosure and thecomparative catalytic converter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure displays a carbon monoxide light-offtemperature within ±1° C. of the hydrocarbon light-off temperature of acatalytic converter made with wet chemistry methods, while the catalyticconverter made with a coated substrate employing at least about 30%less, up to about 30% less, at least about 40% less, up to about 40%less, at least about 50% less, or up to about 50% less catalyst than thecatalytic converter made with wet chemistry methods. In someembodiments, the catalytic converter made with a coated substrate of thepresent disclosure demonstrates this performance after about 50,000 km,about 50,000 miles, about 75,000 km, about 75,000 miles, about 100,000km, about 100,000 miles, about 125,000 km, about 125,000 miles, about150,000 km, or about 150,000 miles of operation (for both the catalyticconverter made with a coated substrate of the present disclosure and thecomparative catalytic converter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure displays a carbon monoxide light-offtemperature within ±5° C. of the nitrogen oxide light-off temperature ofa catalytic converter made with wet chemistry methods, while thecatalytic converter made with a coated substrate employing at leastabout 30% less, up to about 30% less, at least about 40% less, up toabout 40% less, at least about 50% less, or up to about 50% lesscatalyst than the catalytic converter made with wet chemistry methods.In some embodiments, the catalytic converter made with a coatedsubstrate of the present disclosure demonstrates this performance afterabout 50,000 km, about 50,000 miles, about 75,000 km, about 75,000miles, about 100,000 km, about 100,000 miles, about 125,000 km, about125,000 miles, about 150,000 km, or about 150,000 miles of operation(for both the catalytic converter made with a coated substrate of thepresent disclosure and the comparative catalytic converter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure displays a carbon monoxide light-offtemperature within ±4° C. of the nitrogen oxide light-off temperature ofa catalytic converter made with wet chemistry methods, while thecatalytic converter made with a coated substrate employing at leastabout 30% less, up to about 30% less, at least about 40% less, up toabout 40% less, at least about 50% less, or up to about 50% lesscatalyst than the catalytic converter made with wet chemistry methods.In some embodiments, the catalytic converter made with a coatedsubstrate of the present disclosure demonstrates this performance afterabout 50,000 km, about 50,000 miles, about 75,000 km, about 75,000miles, about 100,000 km, about 100,000 miles, about 125,000 km, about125,000 miles, about 150,000 km, or about 150,000 miles of operation(for both the catalytic converter made with a coated substrate of thepresent disclosure and the comparative catalytic converter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure displays a carbon monoxide light-offtemperature within ±3° C. of the nitrogen oxide light-off temperature ofa catalytic converter made with wet chemistry methods, while thecatalytic converter made with a coated substrate employing at leastabout 30% less, up to about 30% less, at least about 40% less, up toabout 40% less, at least about 50% less, or up to about 50% lesscatalyst than the catalytic converter made with wet chemistry methods.In some embodiments, the catalytic converter made with a coatedsubstrate of the present disclosure demonstrates this performance afterabout 50,000 km, about 50,000 miles, about 75,000 km, about 75,000miles, about 100,000 km, about 100,000 miles, about 125,000 km, about125,000 miles, about 150,000 km, or about 150,000 miles of operation(for both the catalytic converter made with a coated substrate of thepresent disclosure and the comparative catalytic converter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure displays a carbon monoxide light-offtemperature within ±2° C. of the nitrogen oxide light-off temperature ofa catalytic converter made with wet chemistry methods, while thecatalytic converter made with a coated substrate employing at leastabout 30% less, up to about 30% less, at least about 40% less, up toabout 40% less, at least about 50% less, or up to about 50% lesscatalyst than the catalytic converter made with wet chemistry methods.In some embodiments, the catalytic converter made with a coatedsubstrate of the present disclosure demonstrates this performance afterabout 50,000 km, about 50,000 miles, about 75,000 km, about 75,000miles, about 100,000 km, about 100,000 miles, about 125,000 km, about125,000 miles, about 150,000 km, or about 150,000 miles of operation(for both the catalytic converter made with a coated substrate of thepresent disclosure and the comparative catalytic converter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure displays a carbon monoxide light-offtemperature within ±1° C. of the nitrogen oxide light-off temperature ofa catalytic converter made with wet chemistry methods, while thecatalytic converter made with a coated substrate employing at leastabout 30% less, up to about 30% less, at least about 40% less, up toabout 40% less, at least about 50% less, or up to about 50% lesscatalyst than the catalytic converter made with wet chemistry methods.In some embodiments, the catalytic converter made with a coatedsubstrate of the present disclosure demonstrates this performance afterabout 50,000 km, about 50,000 miles, about 75,000 km, about 75,000miles, about 100,000 km, about 100,000 miles, about 125,000 km, about125,000 miles, about 150,000 km, or about 150,000 miles of operation(for both the catalytic converter made with a coated substrate of thepresent disclosure and the comparative catalytic converter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure employed on a diesel or gasoline engine ordiesel or gasoline vehicle, such as a light-duty diesel or gasolineengine or light-duty diesel or gasoline vehicle, complies with UnitedStates EPA emissions requirements, while using at least about 30% less,up to about 30% less, at least about 40% less, up to about 40% less, atleast about 50% less, or up to about 50% less, platinum group metal orplatinum group metal loading, as compared to a catalytic converter madewith wet chemistry methods which complies with the same standard. Insome embodiments, the coated substrate is used in a catalytic converter(diesel oxidation catalyst) in the configuration DOC-DPF or DOC-DPF-SCRor in an LNT system to meet or exceed these standards. The emissionsrequirements can be intermediate life requirements or full liferequirements. The requirements can be TLEV requirements, LEVrequirements, or ULEV requirements. In some embodiments, the catalyticconverter made with a coated substrate of the present disclosuredemonstrates any of the foregoing performance standards after about50,000 km, about 50,000 miles, about 75,000 km, about 75,000 miles,about 100,000 km, about 100,000 miles, about 125,000 km, about 125,000miles, about 150,000 km, or about 150,000 miles of operation (for boththe catalytic converter made with a coated substrate of the presentdisclosure and the comparative catalytic converter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure employed on a diesel or gasoline engine ordiesel or gasoline vehicle, such as a light-duty diesel or gasolineengine or light-duty diesel or gasoline vehicle, complies with EPATLEV/LEV intermediate life requirements. In some embodiments, acatalytic converter made with a coated substrate of the presentdisclosure employed on a diesel or gasoline engine or diesel or gasolinevehicle, such as a light-duty diesel or gasoline engine or light-dutydiesel or gasoline vehicle, complies with EPA TLEV/LEV full liferequirements. In some embodiments, a catalytic converter made with acoated substrate of the present disclosure employed on a diesel orgasoline engine or diesel or gasoline vehicle, such as a light-dutydiesel or gasoline engine or light-duty diesel or gasoline vehicle,complies with EPA ULEV intermediate life requirements. In someembodiments, a catalytic converter made with a coated substrate of thepresent disclosure employed on a diesel or gasoline engine or diesel orgasoline vehicle, such as a light-duty diesel or gasoline engine orlight-duty diesel or gasoline vehicle, complies with EPA ULEV full liferequirements. In some embodiments, the coated substrate is used in acatalytic converter (diesel oxidation catalyst) in the configurationDOC-DPF or DOC-DPF-SCR or in an LNT system to meet or exceed thesestandards. In some embodiments, the catalytic converter made with acoated substrate of the present disclosure demonstrates any of theforegoing performance standards after about 50,000 km, about 50,000miles, about 75,000 km, about 75,000 miles, about 100,000 km, about100,000 miles, about 125,000 km, about 125,000 miles, about 150,000 km,or about 150,000 miles of operation.

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure employed on a diesel or gasoline engine ordiesel or gasoline vehicle, such as a light-duty diesel or gasolineengine or light-duty diesel or gasoline vehicle, complies with EPATLEV/LEV intermediate life requirements, while using at least about 30%less, up to about 30% less, at least about 40% less, up to about 40%less, at least about 50% less, or up to about 50% less, platinum groupmetal or platinum group metal loading, as compared to a catalyticconverter made with wet chemistry methods which complies with thatstandard. In some embodiments, a catalytic converter made with a coatedsubstrate of the present disclosure employed on a diesel or gasolineengine or diesel or gasoline vehicle, such as a light-duty diesel orgasoline engine or light-duty diesel or gasoline vehicle, complies withEPA TLEV/LEV full life requirements, while using at least about 30%less, up to about 30% less, at least about 40% less, up to about 40%less, at least about 50% less, or up to about 50% less, platinum groupmetal or platinum group metal loading, as compared to a catalyticconverter made with wet chemistry methods which complies with thatstandard. In some embodiments, a catalytic converter made with a coatedsubstrate of the present disclosure employed on a diesel or gasolineengine or diesel or gasoline vehicle, such as a light-duty diesel vengine or light-duty diesel or gasoline vehicle, complies with EPA ULEVintermediate life requirements, while using at least about 30% less, upto about 30% less, at least about 40% less, up to about 40% less, atleast about 50% less, or up to about 50% less, platinum group metal orplatinum group metal loading, as compared to a catalytic converter madewith wet chemistry methods which complies with that standard. In someembodiments, a catalytic converter made with a coated substrate of thepresent disclosure employed on a diesel or gasoline engine or diesel orgasoline vehicle, such as a light-duty diesel or gasoline engine orlight-duty diesel or gasoline vehicle, complies with EPA ULEV full liferequirements, while using at least about 30% less, up to about 30% less,at least about 40% less, up to about 40% less, at least about 50% less,or up to about 50% less, platinum group metal or platinum group metalloading, as compared to a catalytic converter made with wet chemistrymethods which complies with that standard. In some embodiments, thecoated substrate is used in a catalytic converter (diesel oxidationcatalyst) in the configuration DOC-DPF or DOC-DPF-SCR or in an LNTsystem to meet or exceed these standards. In some embodiments, thecatalytic converter made with a coated substrate of the presentdisclosure demonstrates any of the foregoing performance standards afterabout 50,000 km, about 50,000 miles, about 75,000 km, about 75,000miles, about 100,000 km, about 100,000 miles, about 125,000 km, about125,000 miles, about 150,000 km, or about 150,000 miles of operation(for both the catalytic converter made with a coated substrate of thepresent disclosure and the comparative catalytic converter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure employed on a diesel or gasoline engine ordiesel or gasoline vehicle, such as a light-duty diesel or gasolineengine or light-duty diesel or gasoline vehicle, complies with Euro 5requirements. In some embodiments, a catalytic converter made with acoated substrate of the present disclosure employed on a diesel orgasoline engine or diesel or gasoline vehicle, such as a light-dutydiesel or gasoline engine or light-duty diesel or gasoline vehicle,complies with Euro 6 requirements. In some embodiments, the coatedsubstrate is used in a catalytic converter (diesel oxidation catalyst)in the configuration DOC-DPF or DOC-DPF-SCR or in an LNT system to meetor exceed these standards. In some embodiments, the catalytic convertermade with a coated substrate of the present disclosure demonstrates anyof the foregoing performance standards after about 50,000 km, about50,000 miles, about 75,000 km, about 75,000 miles, about 100,000 km,about 100,000 miles, about 125,000 km, about 125,000 miles, about150,000 km, or about 150,000 miles of operation.

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure employed on a diesel or gasoline engine ordiesel or gasoline vehicle, such as a light-duty diesel or gasolineengine or light-duty diesel or gasoline vehicle, complies with Euro 5requirements, while using at least about 30% less, up to about 30% less,at least about 40% less, up to about 40% less, at least about 50% less,or up to about 50% less, platinum group metal or platinum group metalloading, as compared to a catalytic converter made with wet chemistrymethods which complies with Euro 5 requirements. In some embodiments,the coated substrate is used in a catalytic converter (diesel oxidationcatalyst) in the configuration DOC-DPF or DOC-DPF-SCR or in an LNTsystem to meet or exceed these standards. In some embodiments, thecatalytic converter made with a coated substrate of the presentdisclosure demonstrates any of the foregoing performance standards afterabout 50,000 km, about 50,000 miles, about 75,000 km, about 75,000miles, about 100,000 km, about 100,000 miles, about 125,000 km, about125,000 miles, about 150,000 km, or about 150,000 miles of operation(for both the catalytic converter made with a coated substrate of thepresent disclosure and the comparative catalytic converter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure employed on a diesel or gasoline engine ordiesel or gasoline vehicle, such as a light-duty diesel or gasolineengine or light-duty diesel or gasoline vehicle, complies with Euro 6requirements, while using at least about 30% less, up to about 30% less,at least about 40% less, up to about 40% less, at least about 50% less,or up to about 50% less, platinum group metal or platinum group metalloading, as compared to a catalytic converter made with wet chemistrymethods which complies with Euro 6 requirements. In some embodiments,the coated substrate is used in a catalytic converter (diesel oxidationcatalyst) in the configuration DOC-DPF or DOC-DPF-SCR or in an LNTsystem to meet or exceed these standards. In some embodiments, thecatalytic converter made with a coated substrate of the presentdisclosure demonstrates any of the foregoing performance standards afterabout 50,000 km, about 50,000 miles, about 75,000 km, about 75,000miles, about 100,000 km, about 100,000 miles, about 125,000 km, about125,000 miles, about 150,000 km, or about 150,000 miles of operation(for both the catalytic converter made with a coated substrate of thepresent disclosure and the comparative catalytic converter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure employed on a diesel or gasoline engine ordiesel or gasoline vehicle, such as a light-duty diesel or gasolineengine or light-duty diesel or gasoline vehicle, displays carbonmonoxide emissions of 4200 mg/mile or less. In some embodiments, acatalytic converter made with a coated substrate of the presentdisclosure and employed on a diesel or gasoline engine or diesel orgasoline vehicle, such as a light-duty diesel or gasoline engine orlight-duty diesel or gasoline vehicle, displays carbon monoxideemissions of 3400 mg/mile or less. In some embodiments, a catalyticconverter made with a coated substrate of the present disclosure andemployed on a diesel or gasoline engine or diesel or gasoline vehicle,such as a light-duty diesel or gasoline engine or light-duty diesel orgasoline vehicle, displays carbon monoxide emissions of 2100 mg/mile orless. In another embodiment, a catalytic converter made with a coatedsubstrate of the present disclosure and employed on a diesel or gasolineengine or diesel or gasoline vehicle, such as a light-duty diesel orgasoline engine or light-duty diesel or gasoline vehicle, displayscarbon monoxide emissions of 1700 mg/mile or less. In some embodiments,the coated substrate is used in a catalytic converter (diesel oxidationcatalyst) in the configuration DOC-DPF or DOC-DPF-SCR or in an LNTsystem to meet or exceed these standards. In some embodiments, thecatalytic converter made with a coated substrate of the presentdisclosure demonstrates any of the foregoing performance standards afterabout 50,000 km, about 50,000 miles, about 75,000 km, about 75,000miles, about 100,000 km, about 100,000 miles, about 125,000 km, about125,000 miles, about 150,000 km, or about 150,000 miles of operation.

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure and employed on a diesel or gasoline engine ordiesel or gasoline vehicle, such as a light-duty diesel or gasolineengine or light-duty diesel or gasoline vehicle, displays carbonmonoxide emissions of 500 mg/km or less. In some embodiments, acatalytic converter made with a coated substrate of the presentdisclosure and employed on a diesel or gasoline engine or diesel orgasoline vehicle, such as a light-duty diesel or gasoline engine orlight-duty diesel or gasoline vehicle, displays carbon monoxideemissions of 375 mg/km or less. In some embodiments, a catalyticconverter made with a coated substrate of the present disclosure andemployed on a diesel or gasoline engine or diesel or gasoline vehicle,such as a light-duty diesel or gasoline engine or light-duty diesel orgasoline vehicle, displays carbon monoxide emissions of 250 mg/km orless. In some embodiments, the coated substrate is used in a catalyticconverter (diesel oxidation catalyst) in the configuration DOC-DPF orDOC-DPF-SCR or in an LNT system to meet or exceed these standards. Insome embodiments, the catalytic converter made with a coated substrateof the present disclosure demonstrates any of the foregoing performancestandards after about 50,000 km, about 50,000 miles, about 75,000 km,about 75,000 miles, about 100,000 km, about 100,000 miles, about 125,000km, about 125,000 miles, about 150,000 km, or about 150,000 miles ofoperation.

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure and employed on a diesel or gasoline engine ordiesel or gasoline vehicle, such as a light-duty diesel or gasolineengine or light-duty diesel or gasoline vehicle, displays NO_(x)emissions of 180 mg/km or less. In some embodiments, a catalyticconverter made with a coated substrate of the present disclosure andemployed on a diesel or gasoline engine or diesel or gasoline vehicle,such as a light-duty diesel or gasoline engine or light-duty diesel orgasoline vehicle, displays NO_(x) emissions of 80 mg/km or less. In someembodiments, a catalytic converter made with a coated substrate of thepresent disclosure and employed on a diesel or gasoline engine or dieselor gasoline vehicle, such as a light-duty diesel or gasoline engine orlight-duty diesel or gasoline vehicle, displays NO_(x) emissions of 40mg/km or less. In some embodiments, the coated substrate is used in acatalytic converter (diesel oxidation catalyst) in the configurationDOC-DPF or DOC-DPF-SCR or in an LNT system to meet or exceed thesestandards. In some embodiments, the catalytic converter made with acoated substrate of the present disclosure demonstrates any of theforegoing performance standards after about 50,000 km, about 50,000miles, about 75,000 km, about 75,000 miles, about 100,000 km, about100,000 miles, about 125,000 km, about 125,000 miles, about 150,000 km,or about 150,000 miles of operation.

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure and employed on a diesel or gasoline engine ordiesel or gasoline vehicle, such as a light-duty diesel or gasolineengine or light-duty diesel or gasoline vehicle, displays NO_(x) plus HCemissions of 230 mg/km or less. In some embodiments, a catalyticconverter made with a coated substrate of the present disclosure andemployed on a diesel or gasoline engine or diesel or gasoline vehicle,such as a light-duty diesel or gasoline engine or light-duty diesel orgasoline vehicle, displays NO_(x) plus HC emissions of 170 mg/km orless. In some embodiments, a catalytic converter made with a coatedsubstrate of the present disclosure and employed on a diesel or gasolineengine or diesel or gasoline vehicle, such as a light-duty diesel orgasoline engine or light-duty diesel or gasoline vehicle, displaysNO_(x) plus HC emissions of 85 mg/km or less. In some embodiments, thecoated substrate is used in a catalytic converter (diesel oxidationcatalyst) in the configuration DOC-DPF or DOC-DPF-SCR or in an LNTsystem to meet or exceed these standards. In some embodiments, thecatalytic converter made with a coated substrate of the presentdisclosure demonstrates any of the foregoing performance standards afterabout 50,000 km, about 50,000 miles, about 75,000 km, about 75,000miles, about 100,000 km, about 100,000 miles, about 125,000 km, about125,000 miles, about 150,000 km, or about 150,000 miles of operation.

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure and employed on a diesel or gasoline engine ordiesel or gasoline vehicle, such as a light-duty diesel or gasolineengine or light-duty diesel or gasoline vehicle, displays carbonmonoxide emissions of 500 mg/km or less, while using at least about 30%less, up to about 30% less, at least about 40% less, up to about 40%less, at least about 50% less, or up to about 50% less, platinum groupmetal or platinum group metal loading, as compared to a catalyticconverter made with wet chemistry methods which displays the same orsimilar emissions. In some embodiments, a catalytic converter made witha coated substrate of the present disclosure and employed on a diesel orgasoline engine or diesel or gasoline vehicle, such as a light-dutydiesel or gasoline engine or light-duty diesel or gasoline vehicle,displays carbon monoxide emissions of 375 mg/km or less, while using atleast about 30% less, up to about 30% less, at least about 40% less, upto about 40% less, at least about 50% less, or up to about 50% less,platinum group metal or platinum group metal loading, as compared to acatalytic converter made with wet chemistry methods which displays thesame or similar emissions. In some embodiments, a catalytic convertermade with a coated substrate of the present disclosure and employed on adiesel or gasoline engine or diesel or gasoline vehicle, such as alight-duty diesel or gasoline engine or light-duty diesel or gasolinevehicle, displays carbon monoxide emissions of 250 mg/km or less, whileusing at least about 30% less, up to about 30% less, at least about 40%less, up to about 40% less, at least about 50% less, or up to about 50%less, platinum group metal or platinum group metal loading, as comparedto a catalytic converter made with wet chemistry methods which displaysthe same or similar emissions. In some embodiments, the coated substrateis used in a catalytic converter (diesel oxidation catalyst) in theconfiguration DOC-DPF or DOC-DPF-SCR or in an LNT system to meet orexceed these standards. In some embodiments, the catalytic convertermade with a coated substrate of the present disclosure demonstrates anyof the foregoing performance standards after about 50,000 km, about50,000 miles, about 75,000 km, about 75,000 miles, about 100,000 km,about 100,000 miles, about 125,000 km, about 125,000 miles, about150,000 km, or about 150,000 miles of operation (for both the catalyticconverter made with a coated substrate of the present disclosure and thecomparative catalytic converter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure and employed on a diesel or gasoline engine ordiesel or gasoline vehicle, such as a light-duty diesel or gasolineengine or light-duty diesel or gasoline vehicle, displays NO_(x)emissions of 180 mg/km or less, while using at least about 30% less, upto about 30% less, at least about 40% less, up to about 40% less, atleast about 50% less, or up to about 50% less, platinum group metal orplatinum group metal loading, as compared to a catalytic converter madewith wet chemistry methods which displays the same or similar emissions.In some embodiments, a catalytic converter made with a coated substrateof the present disclosure and employed on a diesel or gasoline engine ordiesel or gasoline vehicle, such as a light-duty diesel or gasolineengine or light-duty diesel or gasoline vehicle, displays NO_(x)emissions of 80 mg/km or less, while using at least about 30% less, upto about 30% less, at least about 40% less, up to about 40% less, atleast about 50% less, or up to about 50% less, platinum group metal orplatinum group metal loading, as compared to a catalytic converter madewith wet chemistry methods which displays the same or similar emissions.In some embodiments, a catalytic converter made with a coated substrateof the present disclosure and employed on a diesel or gasoline engine ordiesel or gasoline vehicle, such as a light-duty diesel or gasolineengine or light-duty diesel or gasoline vehicle, displays NO_(x)emissions of 40 mg/km or less, while using at least about 30% less, upto about 30% less, at least about 40% less, up to about 40% less, atleast about 50% less, or up to about 50% less, platinum group metal orplatinum group metal loading, as compared to a catalytic converter madewith wet chemistry methods which displays the same or similar emissions.In some embodiments, the coated substrate is used in a catalyticconverter (diesel oxidation catalyst) in the configuration DOC-DPF orDOC-DPF-SCR or in an LNT system to meet or exceed these standards. Insome embodiments, the catalytic converter made with a coated substrateof the present disclosure demonstrates any of the foregoing performancestandards after about 50,000 km, about 50,000 miles, about 75,000 km,about 75,000 miles, about 100,000 km, about 100,000 miles, about 125,000km, about 125,000 miles, about 150,000 km, or about 150,000 miles ofoperation (for both the catalytic converter made with a coated substrateof the present disclosure and the comparative catalytic converter).

In some embodiments, a catalytic converter made with a coated substrateof the present disclosure and employed on a diesel or gasoline engine ordiesel or gasoline vehicle, such as a light-duty diesel or gasolineengine or light-duty diesel or gasoline vehicle, displays NO_(x) plus HCemissions of 230 mg/km or less, while using at least about 30% less, upto about 30% less, at least about 40% less, up to about 40% less, atleast about 50% less, or up to about 50% less, platinum group metal orplatinum group metal loading, as compared to a catalytic converter madewith wet chemistry methods which displays the same or similar emissions.In some embodiments, a catalytic converter made with a coated substrateof the present disclosure and employed on a diesel or gasoline engine ordiesel or gasoline vehicle, such as a light-duty diesel or gasolineengine or light-duty diesel or gasoline vehicle, displays NO_(x) plus HCemissions of 170 mg/km or less, while using at least about 30% less, upto about 30% less, at least about 40% less, up to about 40% less, atleast about 50% less, or up to about 50% less, platinum group metal orplatinum group metal loading, as compared to a catalytic converter madewith wet chemistry methods which displays the same or similar emissions.In some embodiments, a catalytic converter made with a coated substrateof the present disclosure and employed on a diesel or gasoline engine ordiesel or gasoline vehicle, such as a light-duty diesel or gasolineengine or light-duty diesel or gasoline vehicle, displays NO_(x) plus HCemissions of 85 mg/km or less, while using at least about 30% less, upto about 30% less, at least about 40% less, up to about 40% less, atleast about 50% less, or up to about 50% less, platinum group metal orplatinum group metal loading, as compared to a catalytic converter madewith wet chemistry methods which displays the same or similar emissions.In some embodiments, the coated substrate is used in a catalyticconverter (diesel oxidation catalyst) in the configuration DOC-DPF orDOC-DPF-SCR or in an LNT system to meet or exceed these standards. Insome embodiments, the catalytic converter made with a coated substrateof the present disclosure demonstrates any of the foregoing performancestandards after about 50,000 km, about 50,000 miles, about 75,000 km,about 75,000 miles, about 100,000 km, about 100,000 miles, about 125,000km, about 125,000 miles, about 150,000 km, or about 150,000 miles ofoperation (for both the catalytic converter made with a coated substrateof the present disclosure and the comparative catalytic converter).

In some embodiments, for the above-described comparisons, the thrifting(reduction) of platinum group metal for the catalytic converters madewith substrates of the present disclosure is compared with either 1) acommercially available catalytic converter, made using wet chemistry,for the application disclosed (e.g., for use on a diesel or gasolineengine or vehicle, such as a light-duty diesel or gasoline engine orlight-duty diesel or gasoline vehicle), or 2) a catalytic converter madewith wet chemistry, which uses the minimal amount of platinum groupmetal to achieve the performance standard indicated.

In some embodiments, for the above-described comparisons, both thecoated substrate according to the present disclosure, and the catalystused in the commercially available catalytic converter or the catalystprepared using wet chemistry methods, are aged (by the same amount)prior to testing. In some embodiments, both the coated substrateaccording to the present disclosure, and the catalyst substrate used inthe commercially available catalytic converter or the catalyst substrateprepared using wet chemistry methods, are aged to about (or up to about)50,000 kilometers, about (or up to about) 50,000 miles, about (or up toabout) 75,000 kilometers, about (or up to about) 75,000 miles, about (orup to about) 100,000 kilometers, about (or up to about) 100,000 miles,about (or up to about) 125,000 kilometers, about (or up to about)125,000 miles, about (or up to about) 150,000 kilometers, or about (orup to about) 150,000 miles. In some embodiments, for the above-describedcomparisons, both the coated substrate according to the presentdisclosure, and the catalyst substrate used in the commerciallyavailable catalytic converter or the catalyst substrate prepared usingwet chemistry methods, are artificially aged (by the same amount) priorto testing. In some embodiments, they are artificially aged by heatingto about 400° C., about 500° C., about 600° C., about 700°, about 800°C., about 900° C., about 1000° C., about 1100° C., or about 1200° C. forabout (or up to about) 4 hours, about (or up to about) 6 hours, about(or up to about) 8 hours, about (or up to about) 10 hours, about (or upto about) 12 hours, about (or up to about) 14 hours, about (or up toabout) 16 hours, about (or up to about) 18 hours, about (or up to about)20 hours, about (or up to about) 22 hours, or about (or up to about) 24hours. In some embodiments, they are artificially aged by heating toabout 800° C. for about 16 hours.

In some embodiments, for the above-described comparisons, the thrifting(reduction) of platinum group metal for the catalytic converters madewith substrates of the present disclosure is compared with either 1) acommercially available catalytic converter, made using wet chemistry,for the application disclosed (e.g., for use on a diesel or gasolineengine or vehicle, such as a light-duty diesel or gasoline engine orlight-duty diesel or gasoline vehicle), or 2) a catalytic converter madewith wet chemistry, which uses the minimal amount of platinum groupmetal to achieve the performance standard indicated, and after thecoated substrate according to the present disclosure and the catalyticsubstrate used in the commercially available catalyst or catalyst madeusing wet chemistry with the minimal amount of PGM to achieve theperformance standard indicated are aged as described above.

In some embodiments, for the above-described catalytic convertersemploying the coated substrates of the present disclosure, for theexhaust treatment systems using catalytic converters employing thecoated substrates of the present disclosure, and for vehicles employingthese catalytic converters and exhaust treatment systems, the catalyticconverter is employed as a diesel oxidation catalyst along with a dieselparticulate filter, or the catalytic converter is employed as a dieseloxidation catalyst along with a diesel particulate filter and aselective catalytic reduction unit, to meet or exceed the standards forCO and/or NO_(x), and/or HC described above.

Exemplary Embodiments

The invention is further described by the following embodiments. Thefeatures of each of the embodiments are combinable with any of the otherembodiments where appropriate and practical.

Embodiment 1

A PNA material comprising: manganese oxide on a first plurality ofmicron-sized support particles; magnesium oxide on a second plurality ofmicron-sized support particles; and calcium oxide on a third pluralityof micron-sized support particles.

Embodiment 2

The PNA material of embodiment 1, wherein manganese oxide, magnesiumoxide, and calcium oxide are nano-sized.

Embodiment 3

The PNA material of any one of embodiments 1-2, wherein the pluralitiesof support particles comprise ceria.

Embodiment 4

The PNA material of embodiment 3, wherein the PNA material comprisesabout 150 g/L to about 350 g/L ceria.

Embodiment 5

The PNA material of any one of embodiments 3-4, wherein the PNA materialcomprises about 1% to about 20% manganese oxide by weight of the amountof ceria.

Embodiment 6

The PNA material of any one of embodiments 3-5, wherein the PNA materialcomprises about 1% to about 10% magnesium oxide by weight of the amountof ceria.

Embodiment 7

The PNA material of any one of embodiments 3-6, wherein the PNA materialcomprises about 1% to about 10% calcium oxide by weight of the amount ofceria.

Embodiment 8

The PNA material of any one of embodiments 3-7, wherein the PNA materialcomprises about 28 g/L manganese oxide.

Embodiment 9

The PNA material of any one of embodiments 3-8, wherein the PNA materialcomprises about 10.5 g/L magnesium oxide.

Embodiment 10

The PNA material of any one of embodiments 3-9, wherein the PNA materialcomprises about 10.5 g/L calcium oxide.

Embodiment 11

The PNA material of any one of embodiments 1-10, wherein the PNAmaterial stores NOx emissions from ambient temperature to about 100° C.

Embodiment 12

The PNA material of any one of embodiments 1-11, wherein the PNAmaterial stores NOx emissions from ambient temperature to about 150° C.

Embodiment 13

The PNA material of any one of embodiments 1-12, wherein the PNAmaterial stores NOx emissions from ambient temperature to about 200° C.

Embodiment 14

The PNA material of any one of embodiments 1-13, further comprisingplatinum group metals.

Embodiment 15

The PNA material of embodiment 14, wherein the platinum group metals areon a fourth plurality of micron-sized support particles.

Embodiment 16

The PNA material of embodiment 14-15, wherein the platinum group metalsare on at least one of the first, second, or third pluralities ofmicron-sized support materials.

Embodiment 17

The PNA material of any one of embodiments 14-16, wherein the platinumgroup metals are added to the support particles using wet chemistrytechniques.

Embodiment 18

The PNA material of embodiment 14-17, wherein the platinum group metalsare added to the support particles using incipient wetness.

Embodiment 19

The PNA material of embodiment 18, wherein the platinum group metalscomprises nano-on-nano particles.

Embodiment 20

The PNA material of any one of embodiments 14-19, wherein the PGMloading is 1.0 g/L to 5.0 g/L.

Embodiment 21

The PNA material of any one of embodiments 14-20, wherein the PGM isplatinum, palladium, or a mixture thereof.

Embodiment 22

A method of forming a PNA material comprising: applying manganese oxideto a first plurality of micron-sized support particles; applyingmagnesium oxide to a second plurality of micron-sized support particles;applying calcium oxide to a third plurality of micron-sized supportparticles; and combining the manganese oxide, magnesium oxide, andcalcium oxide pluralities of micron-sized support particles.

Embodiment 23

The method of embodiment 22, wherein manganese oxide, magnesium oxide,and calcium oxide are nano-sized.

Embodiment 24

The method of any one of embodiments 22-23, wherein the pluralities ofsupport particles comprise ceria.

Embodiment 25

The method of embodiment 24, wherein the PNA material comprises about150 g/L to about 350 g/L ceria.

Embodiment 26

The method of any one of embodiments 24-25, wherein the PNA materialcomprises about 1% to about 20% manganese oxide by weight of the amountof ceria.

Embodiment 27

The method of any one of embodiments 24-26, wherein the PNA materialcomprises about 1% to about 10% magnesium oxide by weight of the amountof ceria.

Embodiment 28

The method of any one of embodiments 24-27, wherein the PNA materialcomprises about 1% to about 10% calcium oxide by weight of the amount ofceria.

Embodiment 29

The method of any one of embodiments 24-28, wherein the PNA materialcomprises about 28 g/L manganese oxide.

Embodiment 30

The method of any one of embodiments 24-29, wherein the PNA materialcomprises about 10.5 g/L magnesium oxide.

Embodiment 31

The method of any one of embodiments 24-30, wherein the PNA materialcomprises about 10.5 g/L calcium oxide.

Embodiment 32

The method of any one of embodiments 22-31, wherein the PNA materialstores NOx emissions from ambient temperature to about 100° C.

Embodiment 33

The method of any one of embodiments 22-32, wherein the PNA materialstores NOx emissions from ambient temperature to about 150° C.

Embodiment 34

The method of any one of embodiments 22-33, wherein the PNA materialstores NOx emissions from ambient temperature to about 200° C.

Embodiment 35

The method of any one of embodiments 22-34, further comprising applyingplatinum group metals to a fourth plurality of micron-sized supportparticles.

Embodiment 36

The method of any one of embodiments 22-35, further comprising applyingplatinum group metals to at least one of the first, second, or thirdpluralities of micron-sized support materials.

Embodiment 37

The method of any one of embodiments 35-36, wherein the platinum groupmetals are applied to the support particles using wet chemistrytechniques.

Embodiment 38

The method of embodiment 35-37, wherein the platinum group metals areapplied to the support particles using incipient wetness.

Embodiment 39

The method of embodiment 38, wherein the platinum group metals comprisesnano-on-nano particles.

Embodiment 40

The method of any one of embodiments 35-39, wherein the PGM loading is1.0 g/L to 5.0 g/L.

Embodiment 41

The method of any one of embodiments 14-20, wherein the PGM is platinum,palladium, or a mixture thereof.

Embodiment 42

A washcoat composition comprising a solids content of: 95% to 98% byweight PNA material comprising manganese oxide on a plurality ofmicron-sized support particles; and 2% to 5% by weight of boehmiteparticles.

Embodiment 43

The washcoat composition of embodiment 42, wherein the 95% to 98% byweight PNA material further comprises magnesium oxide on a secondplurality of micron-sized support particles.

Embodiment 44

The washcoat composition of any one of embodiments 42-43, wherein the95% to 98% by weight PNA material further comprises calcium oxide on athird plurality of micron-sized support particles.

Embodiment 45

A washcoat composition comprising a solids content of: 95% to 98% byweight PNA material comprising magnesium oxide on a plurality ofmicron-sized support particles; and 2% to 5% by weight of boehmiteparticles.

Embodiment 46

The washcoat composition of embodiment 45, wherein the 95% to 98% byweight PNA material further comprises manganese oxide on a secondplurality of micron-sized support particles.

Embodiment 47

The washcoat composition of anyone of embodiments 45-46, wherein the 95%to 98% by weight PNA material further comprises calcium oxide on a thirdplurality of micron-sized support particles.

Embodiment 48

A washcoat composition comprising a solids content of: 95% to 98% byweight PNA material comprising calcium oxide on a plurality ofmicron-sized support particles; and 2% to 5% by weight of boehmiteparticles.

Embodiment 49

The washcoat composition of embodiment 48, wherein the 95% to 98% byweight PNA material further comprises manganese oxide on a secondplurality of micron-sized support particles.

Embodiment 50

The washcoat composition of anyone of embodiments 48-49, wherein the 95%to 98% by weight PNA material further comprises magnesium on a thirdplurality of micron-sized support particles.

Embodiment 51

The washcoat composition of anyone of embodiments 42-50, whereinmanganese oxide, magnesium oxide, and calcium oxide are nano-sized.

Embodiment 52

The washcoat composition of anyone of embodiments 42-51, wherein thepluralities of support particles comprise ceria.

Embodiment 53

The washcoat composition of anyone of embodiments 52, wherein the PNAmaterial comprises about 150 g/L to about 350 g/L ceria.

Embodiment 54

The washcoat composition of anyone of embodiments 52-53, wherein the PNAmaterial comprises about 1% to about 20% manganese oxide by weight ofthe amount of ceria.

Embodiment 55

The washcoat composition of anyone of embodiments 52-54, wherein the PNAmaterial comprises about 1% to about 10% magnesium oxide by weight ofthe amount of ceria.

Embodiment 56

The washcoat composition of anyone of embodiments 52-55, wherein the PNAmaterial comprises about 1% to about 10% calcium oxide by weight of theamount of ceria.

Embodiment 57

The washcoat composition of anyone of embodiments 52-56, wherein the PNAmaterial comprises about 28 g/L manganese oxide.

Embodiment 58

The washcoat composition of anyone of embodiments 52-57, wherein the PNAmaterial comprises about 10.5 g/L magnesium oxide.

Embodiment 59

The washcoat composition of anyone of embodiments 52-58, wherein the PNAmaterial comprises about 10.5 g/L calcium oxide.

Embodiment 60

The washcoat composition of anyone of embodiments 42-59, wherein the PNAmaterial stores NOx emissions from ambient temperature to about 100° C.

Embodiment 61

The washcoat composition of anyone of embodiments 42-60, wherein the PNAmaterial stores NOx emissions from ambient temperature to about 150° C.

Embodiment 62

The washcoat composition of anyone of embodiments 42-61, wherein the PNAmaterial stores NOx emissions from ambient temperature to about 200° C.

Embodiment 63

The washcoat composition of anyone of embodiments 42-62, wherein the PNAmaterial further comprises platinum group metals.

Embodiment 64

The washcoat composition of embodiments 63, wherein the platinum groupmetals are on a fourth plurality of micron-sized support particles.

Embodiment 65

The washcoat composition of anyone of embodiments 63-64, wherein theplatinum group metals are on at least one of the first, second, or thirdpluralities of micron-sized support materials.

Embodiment 66

The washcoat composition of anyone of embodiments 63-65, wherein theplatinum group metals are added to the support particles using wetchemistry techniques.

Embodiment 67

The washcoat composition of anyone of embodiments 63-66, wherein theplatinum group metals are added to the support particles using incipientwetness.

Embodiment 68

The washcoat composition of embodiment 67, wherein the platinum groupmetals comprises nano-on-nano particles.

Embodiment 69

The washcoat composition of anyone of embodiments 63-68, wherein the PGMloading is 1.0 g/L to 5.0 g/L.

Embodiment 70

The washcoat composition of anyone of embodiments 63-69, wherein the PGMis platinum, palladium, or a mixture thereof.

Embodiment 71

The washcoat composition of anyone of embodiments 42-70, wherein thesolids are suspended in an aqueous medium at a pH between 3 and 5.

Embodiment 72

A coated substrate comprising: a substrate; a washcoat layer comprisingzeolite particles; a washcoat layer comprising a PNA material; and awashcoat layer comprising catalytically active particles, wherein thecatalytically active particles comprise composite nano-particles bondedto micron-sized carrier particles, and the composite nano-particlescomprise a support nano-particle and a catalytic nano-particle.

Embodiment 73

The coated substrate of embodiment 72, wherein the PNA materialcomprises manganese oxide on a plurality of micron-sized supportparticles.

Embodiment 74

The coated substrate of any one of embodiments 72-73, wherein the PNAmaterial comprises magnesium oxide on a plurality of micron-sizedsupport particles.

Embodiment 75

The coated substrate of any one of embodiments 72-74, wherein the PNAmaterial comprises calcium oxide on a plurality of micron-sized supportparticles.

Embodiment 76

The coated substrate of any one of embodiments 72-75, wherein the PNAmaterial comprises manganese oxide, magnesium oxide, and calcium oxideon different pluralities of micron-sized support particles.

Embodiment 77

The coated substrate of any one of embodiments 73-76, wherein themanganese oxide, magnesium oxide, and calcium oxide are nano-sized.

Embodiment 78

The coated substrate of any one of embodiments 73-76, wherein thepluralities of support particles comprise ceria.

Embodiment 79

The coated substrate of any one of embodiments 78, wherein the PNAmaterial comprises about 150 g/L to about 350 g/L ceria.

Embodiment 80

The coated substrate of any one of embodiments 78-79, wherein the PNAmaterial comprises about 1% to about 20% manganese oxide by weight ofthe amount of ceria.

Embodiment 81

The coated substrate of any one of embodiments 78-80, wherein the PNAmaterial comprises about 1% to about 10% magnesium oxide by weight ofthe amount of ceria.

Embodiment 82

The coated substrate of any one of embodiments 78-81, wherein the PNAmaterial comprises about 1% to about 10% calcium oxide by weight of theamount of ceria.

Embodiment 83

The coated substrate of any one of embodiments 78-82, wherein the PNAmaterial comprises about 28 g/L manganese oxide.

Embodiment 84

The coated substrate of any one of embodiments 78-83, wherein the PNAmaterial comprises about 10.5 g/L magnesium oxide.

Embodiment 85

The coated substrate of any one of embodiments 78-84, wherein the PNAmaterial comprises about 10.5 g/L calcium oxide.

Embodiment 86

The coated substrate of any one of embodiments 72-85, wherein the PNAmaterial stores NOx emissions from ambient temperature to about 100° C.

Embodiment 87

The coated substrate of any one of embodiments 72-86, wherein the PNAmaterial stores NOx emissions from ambient temperature to about 150° C.

Embodiment 88

The coated substrate of any one of embodiments 72-87, wherein the PNAmaterial stores NOx emissions from ambient temperature to about 200° C.

Embodiment 89

The coated substrate of any one of embodiments 72-88, wherein thewashcoat layer comprising the PNA material further comprises boehmiteparticles.

Embodiment 90

The coated substrate of any one of embodiments 72-89, wherein the PNAmaterial comprises 95% to 98% by weight of the mixture of PNA materialand boehmite particles in the washcoat layer comprising PNA material.

Embodiment 91

The coated substrate of any one of embodiments 72-90, wherein theboehmite particles comprise 2% to 5% by weight of the mixture of PNAmaterial and boehmite particles in the washcoat layer comprising PNAmaterial.

Embodiment 92

The coated substrate of any one of embodiments 72-91, wherein thecatalytic nano-particles comprise at least one platinum group metal.

Embodiment 93

The coated substrate of any one of embodiments 72-92, wherein thecatalytic nano-particles comprise platinum and palladium.

Embodiment 94

The coated substrate of any one of embodiments 72-93, wherein thecatalytic nano-particles comprise platinum and palladium in a weightratio of 2:1 platinum:palladium

Embodiment 95

The coated substrate of any one of embodiments 72-94, wherein thesupport nano-particles have an average diameter of 10 nm to 20 nm.

Embodiment 96

The coated substrate of any one of embodiments 72-95, wherein thecatalytic nano-particles have an average diameter of between 1 nm and 5nm.

Embodiment 97

The coated substrate of any one of embodiments 72-96, wherein thewashcoat layer comprising zeolite particles comprises metal-oxideparticles and boehmite particles.

Embodiment 98

The coated substrate of any one of embodiments 72-97, wherein themetal-oxide particles are aluminum-oxide particles.

Embodiment 99

The coated substrate of any one of embodiments 97-98, wherein thezeolite particles comprise 60% to 80% by weight of the mixture ofzeolite particles, metal-oxide particles, and boehmite particles in thewashcoat layer comprising zeolite particles.

Embodiment 100

The coated substrate of any one of embodiments 97-99, wherein theboehmite particles comprise 2% to 5% by weight of the mixture of zeoliteparticles, metal-oxide particles, and boehmite particles in the washcoatlayer comprising zeolite particles.

Embodiment 101

The coated substrate of embodiment 97-100, wherein the metal-oxideparticles comprise 15% to 38% by weight of the mixture of zeoliteparticles, metal-oxide particles, and boehmite particles in the washcoatlayer comprising zeolite particles.

Embodiment 102

The coated substrate of any one of embodiments 72-101, wherein thewashcoat layer comprising zeolite particles does not include platinumgroup metals.

Embodiment 103

The coated substrate of any one of embodiments 72-102, wherein thezeolite particles in the washcoat layer comprising zeolite particleseach have a diameter of 0.2 microns to 8 microns.

Embodiment 104

The coated substrate of any one of embodiments 72-103, wherein thewashcoat layer comprising catalytically active particles furthercomprises boehmite particles and silica particles.

Embodiment 105

The coated substrate of any one of embodiments 72-104, wherein thewashcoat layer comprising catalytically active particles issubstantially free of zeolites

Embodiment 106

The coated substrate of any one of embodiments 72-105, wherein thecatalytically active particles comprise 35% to 95% by weight of thecombination of the catalytically active particles, boehmite particles,and silica particles in the washcoat layer comprising catalyticallyactive particles.

Embodiment 107

The coated substrate of any one of embodiments 72-106, wherein thesilica particles are present in an amount up to 20% by weight of thecombination of the catalytically active particles, boehmite particles,and silica particles in the washcoat layer comprising catalyticallyactive particles

Embodiment 108

The coated substrate of any one of embodiments 72-107, wherein theboehmite particles comprise 2% to 5% by weight of the combination of thecatalytically active particles, the boehmite particles, and the silicaparticles in the washcoat layer comprising catalytically activeparticles

Embodiment 109

The coated substrate of any one of embodiments 72-108, wherein thewashcoat layer comprising catalytically active particles comprises 92%by weight of the catalytically active particles, 3% by weight of theboehmite particles, and 5% by weight of the silica particles

Embodiment 110

The coated substrate of any one of embodiments 72-109, wherein thesubstrate comprises cordierite.

Embodiment 111

The coated substrate of any one of embodiments 72-110, wherein thesubstrate comprises a honeycomb structure.

Embodiment 112

The coated substrate of any one of embodiments 72-111, wherein thewashcoat layer comprising zeolite particles has a thickness of 25 g/l to90 g/l.

Embodiment 113

The coated substrate of any one of embodiments 72-112, wherein thewashcoat layer comprising catalytically active particles has a thicknessof 50 g/l to 250 g/l.

Embodiment 114

The coated substrate of any one of embodiments 72-113, furthercomprising a corner-fill layer deposited directly on the substrate.

Embodiment 115

The coated substrate of any one of embodiments 72-114, wherein thecoated substrate has a platinum group metal loading of 4 g/l or less anda light-off temperature for carbon monoxide at least 5° C. lower thanthe light-off temperature of a substrate with the same platinum groupmetal loading deposited by wet-chemistry methods.

Embodiment 116

The coated substrate of any one of embodiments 72-115, wherein thecoated substrate has a platinum group metal loading of about 1.0 g/l toabout 4.0 g/l.

Embodiment 117

The coated substrate of any one of embodiments 72-116, said coatedsubstrate having a platinum group metal loading of about 1.0 g/l toabout 5.5 g/l, wherein after 125,000 miles of operation in a vehicularcatalytic converter, the coated substrate has a light-off temperaturefor carbon monoxide at least 5° C. lower than a coated substrateprepared by depositing platinum group metals by wet chemical methodshaving the same platinum group metal loading after 125,000 miles ofoperation in a vehicular catalytic converter.

Embodiment 118

The coated substrate of any one of embodiments 72-117, said coatedsubstrate having a platinum group metal loading of about 1.0 g/l toabout 5.5 g/l, wherein after aging for 16 hours at 800° C., the coatedsubstrate has a light-off temperature for carbon monoxide at least 5° C.lower than a coated substrate prepared by depositing platinum groupmetals by wet chemical methods having the same platinum group metalloading after aging for 16 hours at 800° C.

Embodiment 119

A catalytic converter comprising a coated substrate of any one ofembodiments 72-118.

Embodiment 120

An exhaust treatment system comprising a conduit for exhaust gas and acatalytic converter according to embodiment 119.

Embodiment 121

A vehicle comprising a catalytic converter according to embodiment 119.

Embodiment 122

A diesel vehicle comprising a catalytic converter according toembodiment 119.

Embodiment 123

The diesel vehicle of embodiment 122, wherein the diesel vehicle is alight-duty diesel vehicle.

Embodiment 124

A method of treating an exhaust gas, comprising contacting the coatedsubstrate of any one of embodiments 72-118 with the exhaust gas.

Embodiment 125

A method of treating an exhaust gas, comprising contacting the coatedsubstrate of any one of embodiments 72-118 with the exhaust gas, whereinthe substrate is housed within a catalytic converter configured toreceive the exhaust gas.

Embodiment 126

A coated substrate comprising: a substrate; a washcoat layer comprisingzeolite particles and a PNA material; and a washcoat layer comprisingcatalytically active particles, wherein the catalytically activeparticles comprise composite nano-particles bonded to micron-sizedcarrier particles, and the composite nano-particles comprise a supportnano-particle and a catalytic nano-particle.

Embodiment 127

The coated substrate of embodiment 126, wherein the PNA materialcomprises manganese oxide on a plurality of micron-sized supportparticles.

Embodiment 128

The coated substrate of any one of embodiments 126-127, wherein the PNAmaterial comprises magnesium oxide on a plurality of micron-sizedsupport particles.

Embodiment 129

The coated substrate of any one of embodiments 126-128, wherein the PNAmaterial comprises calcium oxide on a plurality of micron-sized supportparticles.

Embodiment 130

The coated substrate of any one of embodiments 126-129, wherein the PNAmaterial comprises manganese oxide, magnesium oxide, and calcium oxideon different pluralities of micron-sized support particles.

Embodiment 131

The coated substrate of any one of embodiments 126-130, wherein themanganese oxide, magnesium oxide, and calcium oxide are nano-sized.

Embodiment 132

The coated substrate of any one of embodiments 126-131, wherein thepluralities of support particles comprise ceria.

Embodiment 133

The coated substrate of any one of embodiments 132, wherein the PNAmaterial comprises about 150 g/L to about 350 g/L ceria.

Embodiment 134

The coated substrate of any one of embodiments 132-133, wherein the PNAmaterial comprises about 1% to about 20% manganese oxide by weight ofthe amount of ceria.

Embodiment 135

The coated substrate of any one of embodiments 132-134, wherein the PNAmaterial comprises about 1% to about 10% magnesium oxide by weight ofthe amount of ceria.

Embodiment 136

The coated substrate of any one of embodiments 132-135, wherein the PNAmaterial comprises about 1% to about 10% calcium oxide by weight of theamount of ceria.

Embodiment 137

The coated substrate of any one of embodiments 132-136, wherein the PNAmaterial comprises about 28 g/L manganese oxide.

Embodiment 138

The coated substrate of any one of embodiments 132-137, wherein the PNAmaterial comprises about 10.5 g/L magnesium oxide.

Embodiment 139

The coated substrate of any one of embodiments 132-138, wherein the PNAmaterial comprises about 10.5 g/L calcium oxide.

Embodiment 140

The coated substrate of any one of embodiments 126-139, wherein the PNAmaterial stores NOx emissions from ambient temperature to about 100° C.

Embodiment 141

The coated substrate of any one of embodiments 126-140, wherein the PNAmaterial stores NOx emissions from ambient temperature to about 150° C.

Embodiment 142

The coated substrate of any one of embodiments 126-141, wherein the PNAmaterial stores NOx emissions from ambient temperature to about 200° C.

Embodiment 143

The coated substrate of any one of embodiments 126-142, wherein thecatalytic nano-particles comprise at least one platinum group metal.

Embodiment 144

The coated substrate of any one of embodiments 126-143, wherein thecatalytic nano-particles comprise platinum and palladium.

Embodiment 145

The coated substrate of any one of embodiments 126-144, wherein thecatalytic nano-particles comprise platinum and palladium in a weightratio of 2:1 platinum:palladium

Embodiment 146

The coated substrate of any one of embodiments 126-145, wherein thesupport nano-particles have an average diameter of 10 nm to 20 nm.

Embodiment 147

The coated substrate of any one of embodiments 126-146, wherein thecatalytic nano-particles have an average diameter of between 1 nm and 5nm.

Embodiment 148

The coated substrate of any one of embodiments 126-147, wherein thewashcoat layer comprising zeolite particles and PNA material furthercomprises metal-oxide particles and boehmite particles.

Embodiment 149

The coated substrate of any one of embodiments 126-148, wherein themetal-oxide particles are aluminum-oxide particles.

Embodiment 150

The coated substrate of any one of embodiments 126-149, wherein theboehmite particles comprise 2% to 5% by weight of the mixture of zeoliteparticles, metal-oxide particles, and boehmite particles in the washcoatlayer comprising zeolite particles and PNA material.

Embodiment 151

The coated substrate of any one of embodiments 126-150, wherein themetal-oxide particles comprise 15% to 38% by weight of the mixture ofzeolite particles, metal-oxide particles, and boehmite particles in thewashcoat layer comprising zeolite particles and PNA material.

Embodiment 152

The coated substrate of any one of embodiments 126-151, wherein thewashcoat layer comprising zeolite particles and PNA material does notinclude platinum group metals.

Embodiment 153

The coated substrate of any one of embodiments 126-152, wherein thezeolite particles in the washcoat layer comprising zeolite particles andPNA material each have a diameter of 0.2 microns to 8 microns.

Embodiment 154

The coated substrate of any one of embodiments 126-153, wherein thewashcoat layer comprising catalytically active particles furthercomprises boehmite particles and silica particles.

Embodiment 155

The coated substrate of any one of embodiments 126-154, wherein thewashcoat layer comprising catalytically active particles issubstantially free of zeolites

Embodiment 156

The coated substrate of any one of embodiments 126-155, wherein thecatalytically active particles comprise 35% to 95% by weight of thecombination of the catalytically active particles, boehmite particles,and silica particles in the washcoat layer comprising catalyticallyactive particles.

Embodiment 157

The coated substrate of any one of embodiments 126-156, wherein thesilica particles are present in an amount up to 20% by weight of thecombination of the catalytically active particles, boehmite particles,and silica particles in the washcoat layer comprising catalyticallyactive particles

Embodiment 158

The coated substrate of any one of embodiments 126-157, wherein theboehmite particles comprise 2% to 5% by weight of the combination of thecatalytically active particles, the boehmite particles, and the silicaparticles in the washcoat layer comprising catalytically activeparticles

Embodiment 159

The coated substrate of any one of embodiments 126-158, wherein thewashcoat layer comprising catalytically active particles comprises 92%by weight of the catalytically active particles, 3% by weight of theboehmite particles, and 5% by weight of the silica particles

Embodiment 160

The coated substrate of any one of embodiments 126-159, wherein thesubstrate comprises cordierite.

Embodiment 161

The coated substrate of any one of embodiments 126-160, wherein thesubstrate comprises a honeycomb structure.

Embodiment 162

The coated substrate of any one of embodiments 126-161, wherein thewashcoat layer comprising catalytically active particles has a thicknessof 50 g/l to 250 g/l.

Embodiment 163

The coated substrate of any one of embodiments 126-162, furthercomprising a corner-fill layer deposited directly on the substrate.

Embodiment 164

The coated substrate of any one of embodiments 126-163, wherein thecoated substrate has a platinum group metal loading of 4 g/l or less anda light-off temperature for carbon monoxide at least 5° C. lower thanthe light-off temperature of a substrate with the same platinum groupmetal loading deposited by wet-chemistry methods.

Embodiment 165

The coated substrate of any one of embodiments 126-164, wherein thecoated substrate has a platinum group metal loading of about 1.0 g/l toabout 4.0 g/l.

Embodiment 166

The coated substrate of any one of embodiments 126-165, said coatedsubstrate having a platinum group metal loading of about 1.0 g/l toabout 5.5 g/l, wherein after 125,000 miles of operation in a vehicularcatalytic converter, the coated substrate has a light-off temperaturefor carbon monoxide at least 5° C. lower than a coated substrateprepared by depositing platinum group metals by wet chemical methodshaving the same platinum group metal loading after 125,000 miles ofoperation in a vehicular catalytic converter.

Embodiment 167

The coated substrate of any one of embodiments 126-166, said coatedsubstrate having a platinum group metal loading of about 1.0 g/l toabout 5.5 g/l, wherein after aging for 16 hours at 800° C., the coatedsubstrate has a light-off temperature for carbon monoxide at least 5° C.lower than a coated substrate prepared by depositing platinum groupmetals by wet chemical methods having the same platinum group metalloading after aging for 16 hours at 800° C.

Embodiment 168

A catalytic converter comprising a coated substrate of any one ofembodiments 126-167.

Embodiment 169

An exhaust treatment system comprising a conduit for exhaust gas and acatalytic converter according to embodiment 168.

Embodiment 170

A vehicle comprising a catalytic converter according to embodiment 168.

Embodiment 171

A diesel vehicle comprising a catalytic converter according toembodiment 168.

Embodiment 172

The diesel vehicle of embodiment 171, wherein the diesel vehicle is alight-duty diesel vehicle.

Embodiment 173

A method of treating an exhaust gas, comprising contacting the coatedsubstrate of any one of embodiments 126-167 with the exhaust gas.

Embodiment 174

A method of treating an exhaust gas, comprising contacting the coatedsubstrate of any one of embodiments 126-167 with the exhaust gas,wherein the substrate is housed within a catalytic converter configuredto receive the exhaust gas.

Embodiment 175

A coated substrate comprising: a substrate; a washcoat layer comprisingzeolite particles, a PNA material, and catalytically active particles,wherein the catalytically active particles comprise compositenano-particles bonded to micron-sized carrier particles, and thecomposite nano-particles comprise a support nano-particle and acatalytic nano-particle.

Embodiment 176

A method of forming a coated substrate comprising: coating a substratewith a washcoat composition comprising zeolite particles; coating thesubstrate with a washcoat composition comprising a PNA material; andcoating the substrate with a washcoat composition comprisingcatalytically active particles, wherein the catalytically activeparticles comprise composite nano-particles bonded to micron-sizedcarrier particles, and the composite nano-particles comprise a supportnano-particle and a catalytic nano-particle.

Embodiment 177

The method of embodiment 176, wherein the PNA material comprisesmanganese oxide on a plurality of micron-sized support particles.

Embodiment 178

The method of any one of embodiments 176-177, wherein the PNA materialcomprises magnesium oxide on a plurality of micron-sized supportparticles.

Embodiment 179

The method of any one of embodiments 176-178, wherein the PNA materialcomprises calcium oxide on a plurality of micron-sized supportparticles.

Embodiment 180

The method of any one of embodiments 176-179, wherein the PNA materialcomprises manganese oxide, magnesium oxide, and calcium oxide ondifferent pluralities of micron-sized support particles.

Embodiment 181

The method of any one of embodiments 176-180, wherein the manganeseoxide, magnesium oxide, and calcium oxide are nano-sized.

Embodiment 182

The method of any one of embodiments 176-181, wherein the pluralities ofsupport particles comprise ceria.

Embodiment 183

The method of any one of embodiments 176-182, wherein the PNA materialcomprises about 150 g/L to about 350 g/L ceria.

Embodiment 184

The method of any one of embodiments 176-183, wherein the PNA materialcomprises about 1% to about 20% manganese oxide by weight of the amountof ceria.

Embodiment 185

The method of any one of embodiments 176-184, wherein the PNA materialcomprises about 1% to about 10% magnesium oxide by weight of the amountof ceria.

Embodiment 186

The method of any one of embodiments 176-185, wherein the PNA materialcomprises about 1% to about 10% calcium oxide by weight of the amount ofceria.

Embodiment 187

The method of any one of embodiments 176-186, wherein the PNA materialcomprises about 28 g/L manganese oxide.

Embodiment 188

The method of any one of embodiments 176-187, wherein the PNA materialcomprises about 10.5 g/L magnesium oxide.

Embodiment 189

The method of any one of embodiments 176-188, wherein the PNA materialcomprises about 10.5 g/L calcium oxide.

Embodiment 190

The method of any one of embodiments 176-189, wherein the PNA materialstores NOx emissions from ambient temperature to about 100° C.

Embodiment 191

The method of any one of embodiments 176-190, wherein the PNA materialstores NOx emissions from ambient temperature to about 150° C.

Embodiment 192

The method of any one of embodiments 176-191, wherein the PNA materialstores NOx emissions from ambient temperature to about 200° C.

Embodiment 193

The method of any one of embodiments 176-192, wherein the washcoat layercomprising the PNA material further comprises boehmite particles.

Embodiment 194

The method of any one of embodiments 176-193, wherein the PNA materialcomprises 95% to 98% by weight of the mixture of PNA material andboehmite particles in the washcoat layer comprising PNA material.

Embodiment 195

The method of any one of embodiments 176-194, wherein the boehmiteparticles comprise 2% to 5% by weight of the mixture of PNA material andboehmite particles in the washcoat layer comprising PNA material.

Embodiment 196

The method of any one of embodiments 176-195, wherein the catalyticnano-particles comprise at least one platinum group metal.

Embodiment 197

The method of any one of embodiments 176-196, wherein the catalyticnano-particles comprise platinum and palladium.

Embodiment 198

The method of any one of embodiments 176-197, wherein the catalyticnano-particles comprise platinum and palladium in a weight ratio of 2:1platinum:palladium

Embodiment 199

The method of any one of embodiments 176-198, wherein the supportnano-particles have an average diameter of 10 nm to 20 nm.

Embodiment 200

The method of any one of embodiments 176-199, wherein the catalyticnano-particles have an average diameter of between 1 nm and 5 nm.

Embodiment 201

The method of any one of embodiments 176-200, wherein the washcoat layercomprising zeolite particles comprises metal-oxide particles andboehmite particles.

Embodiment 202

The method of any one of embodiments 201, wherein the metal-oxideparticles are aluminum-oxide particles.

Embodiment 203

The method of any one of embodiments 201-202, wherein the zeoliteparticles comprise 60% to 80% by weight of the mixture of zeoliteparticles, metal-oxide particles, and boehmite particles in the washcoatlayer comprising zeolite particles.

Embodiment 204

The method of any one of embodiments 201-203, wherein the boehmiteparticles comprise 2% to 5% by weight of the mixture of zeoliteparticles, metal-oxide particles, and boehmite particles in the washcoatlayer comprising zeolite particles.

Embodiment 205

The method of embodiment 201-204, wherein the metal-oxide particlescomprise 15% to 38% by weight of the mixture of zeolite particles,metal-oxide particles, and boehmite particles in the washcoat layercomprising zeolite particles.

Embodiment 206

The method of any one of embodiments 176-205, wherein the washcoat layercomprising zeolite particles does not include platinum group metals.

Embodiment 207

The method of any one of embodiments 176-206, wherein the zeoliteparticles in the washcoat layer comprising zeolite particles each have adiameter of 0.2 microns to 8 microns.

Embodiment 208

The method of any one of embodiments 176-207, wherein the washcoat layercomprising catalytically active particles further comprises boehmiteparticles and silica particles.

Embodiment 209

The method of any one of embodiments 176-208, wherein the washcoat layercomprising catalytically active particles is substantially free ofzeolites

Embodiment 210

The method of any one of embodiments 176-209, wherein the catalyticallyactive particles comprise 35% to 95% by weight of the combination of thecatalytically active particles, boehmite particles, and silica particlesin the washcoat layer comprising catalytically active particles.

Embodiment 211

The method of any one of embodiments 176-210, wherein the silicaparticles are present in an amount up to 20% by weight of thecombination of the catalytically active particles, boehmite particles,and silica particles in the washcoat layer comprising catalyticallyactive particles

Embodiment 212

The method of any one of embodiments 176-211, wherein the boehmiteparticles comprise 2% to 5% by weight of the combination of thecatalytically active particles, the boehmite particles, and the silicaparticles in the washcoat layer comprising catalytically activeparticles

Embodiment 213

The method of any one of embodiments 176-212, wherein the washcoat layercomprising catalytically active particles comprises 92% by weight of thecatalytically active particles, 3% by weight of the boehmite particles,and 5% by weight of the silica particles

Embodiment 214

The method of any one of embodiments 176-213, wherein the substratecomprises cordierite.

Embodiment 215

The method of any one of embodiments 176-214, wherein the substratecomprises a honeycomb structure.

Embodiment 216

The method of any one of embodiments 176-215, wherein the washcoat layercomprising zeolite particles has a thickness of 25 g/l to 90 g/l.

Embodiment 217

The method of any one of embodiments 176-216, wherein the washcoat layercomprising catalytically active particles has a thickness of 50 g/l to250 g/l.

Embodiment 218

The method of any one of embodiments 176-217, further comprisingdepositing a corner-fill layer directly on the substrate.

Embodiment 219

The method of any one of embodiments 176-218, wherein the coatedsubstrate has a platinum group metal loading of 4 g/l or less and alight-off temperature for carbon monoxide at least 5° C. lower than thelight-off temperature of a substrate with the same platinum group metalloading deposited by wet-chemistry methods.

Embodiment 220

The method of any one of embodiments 176-219, wherein the coatedsubstrate has a platinum group metal loading of about 1.0 g/l to about4.0 g/l.

Embodiment 221

The method of any one of embodiments 176-220, said coated substratehaving a platinum group metal loading of about 1.0 g/l to about 5.5 g/l,wherein after 125,000 miles of operation in a vehicular catalyticconverter, the coated substrate has a light-off temperature for carbonmonoxide at least 5° C. lower than a coated substrate prepared bydepositing platinum group metals by wet chemical methods having the sameplatinum group metal loading after 125,000 miles of operation in avehicular catalytic converter.

Embodiment 222

The method of any one of embodiments 176-221, said coated substratehaving a platinum group metal loading of about 1.0 g/l to about 5.5 g/l,wherein after aging for 16 hours at 800° C., the coated substrate has alight-off temperature for carbon monoxide at least 5° C. lower than acoated substrate prepared by depositing platinum group metals by wetchemical methods having the same platinum group metal loading afteraging for 16 hours at 800° C.

Embodiment 223

A method of forming a coated substrate comprising: coating a substratewith a washcoat composition comprising zeolite particles and a PNAmaterial; and coating the substrate with a washcoat compositioncomprising catalytically active particles, wherein the catalyticallyactive particles comprise composite nano-particles bonded tomicron-sized carrier particles, and the composite nano-particlescomprise a support nano-particle and a catalytic nano-particle.

Embodiment 224

The method of embodiment 223, wherein the PNA material comprisesmanganese oxide on a plurality of micron-sized support particles.

Embodiment 225

The method of any one of embodiments 223-224, wherein the PNA materialcomprises magnesium oxide on a plurality of micron-sized supportparticles.

Embodiment 226

The method of any one of embodiments 223-225, wherein the PNA materialcomprises calcium oxide on a plurality of micron-sized supportparticles.

Embodiment 227

The method of any one of embodiments 223-226, wherein the PNA materialcomprises manganese oxide, magnesium oxide, and calcium oxide ondifferent pluralities of micron-sized support particles.

Embodiment 228

The method of any one of embodiments 224-227, wherein the manganeseoxide, magnesium oxide, and calcium oxide are nano-sized.

Embodiment 229

The method of any one of embodiments 224-228, wherein the pluralities ofsupport particles comprise ceria.

Embodiment 230

The method of any one of embodiments 229, wherein the PNA materialcomprises about 150 g/L to about 350 g/L ceria.

Embodiment 231

The method of any one of embodiments 229-230, wherein the PNA materialcomprises about 1% to about 20% manganese oxide by weight of the amountof ceria.

Embodiment 232

The method of any one of embodiments 229-231, wherein the PNA materialcomprises about 1% to about 10% magnesium oxide by weight of the amountof ceria.

Embodiment 233

The method of any one of embodiments 229-232, wherein the PNA materialcomprises about 1% to about 10% calcium oxide by weight of the amount ofceria.

Embodiment 234

The method of any one of embodiments 229-233, wherein the PNA materialcomprises about 28 g/L manganese oxide.

Embodiment 235

The method of any one of embodiments 229-234, wherein the PNA materialcomprises about 10.5 g/L magnesium oxide.

Embodiment 236

The method of any one of embodiments 229-235, wherein the PNA materialcomprises about 10.5 g/L calcium oxide.

Embodiment 237

The method of any one of embodiments 223-236, wherein the PNA materialstores NOx emissions from ambient temperature to about 100° C.

Embodiment 238

The method of any one of embodiments 223-237, wherein the PNA materialstores NOx emissions from ambient temperature to about 150° C.

Embodiment 239

The method of any one of embodiments 223-238, wherein the PNA materialstores NOx emissions from ambient temperature to about 200° C.

Embodiment 240

The method of any one of embodiments 223-239, wherein the catalyticnano-particles comprise at least one platinum group metal.

Embodiment 241

The method of any one of embodiments 223-240, wherein the catalyticnano-particles comprise platinum and palladium.

Embodiment 242

The method of any one of embodiments 223-241, wherein the catalyticnano-particles comprise platinum and palladium in a weight ratio of 2:1platinum:palladium

Embodiment 243

The method of any one of embodiments 223-242, wherein the supportnano-particles have an average diameter of 10 nm to 20 nm.

Embodiment 244

The method of any one of embodiments 223-243, wherein the catalyticnano-particles have an average diameter of between 1 nm and 5 nm.

Embodiment 245

The method of any one of embodiments 223-244, wherein the washcoat layercomprising zeolite particles and PNA material further comprisesmetal-oxide particles and boehmite particles.

Embodiment 246

The method of any one of embodiments 245, wherein the metal-oxideparticles are aluminum-oxide particles.

Embodiment 247

The method of any one of embodiments 245-246, wherein the zeoliteparticles comprise 60% to 80% by weight of the mixture of zeoliteparticles, metal-oxide particles, and boehmite particles in the washcoatlayer comprising zeolite particles and PNA material.

Embodiment 248

The method of any one of embodiments 245-247, wherein the boehmiteparticles comprise 2% to 5% by weight of the mixture of zeoliteparticles, metal-oxide particles, and boehmite particles in the washcoatlayer comprising zeolite particles and PNA material.

Embodiment 249

The method of embodiment 245-248, wherein the metal-oxide particlescomprise 15% to 38% by weight of the mixture of zeolite particles,metal-oxide particles, and boehmite particles in the washcoat layercomprising zeolite particles and PNA material.

Embodiment 250

The method of any one of embodiments 140-164, wherein the washcoat layercomprising zeolite particles and PNA material does not include platinumgroup metals.

Embodiment 251

The method of any one of embodiments 140-165, wherein the zeoliteparticles in the washcoat layer comprising zeolite particles and PNAmaterial each have a diameter of 0.2 microns to 8 microns.

Embodiment 252

The method of any one of embodiments 223-251, wherein the washcoat layercomprising catalytically active particles further comprises boehmiteparticles and silica particles.

Embodiment 253

The method of any one of embodiments 223-252, wherein the washcoat layercomprising catalytically active particles is substantially free ofzeolites

Embodiment 254

The method of any one of embodiments 223-253, wherein the catalyticallyactive particles comprise 35% to 95% by weight of the combination of thecatalytically active particles, boehmite particles, and silica particlesin the washcoat layer comprising catalytically active particles.

Embodiment 255

The method of any one of embodiments 223-254, wherein the silicaparticles are present in an amount up to 20% by weight of thecombination of the catalytically active particles, boehmite particles,and silica particles in the washcoat layer comprising catalyticallyactive particles

Embodiment 256

The method of any one of embodiments 223-255, wherein the boehmiteparticles comprise 2% to 5% by weight of the combination of thecatalytically active particles, the boehmite particles, and the silicaparticles in the washcoat layer comprising catalytically activeparticles

Embodiment 257

The method of any one of embodiments 223-256, wherein the washcoat layercomprising catalytically active particles comprises 92% by weight of thecatalytically active particles, 3% by weight of the boehmite particles,and 5% by weight of the silica particles

Embodiment 258

The method of any one of embodiments 223-257, wherein the substratecomprises cordierite.

Embodiment 259

The method of any one of embodiments 223-258, wherein the substratecomprises a honeycomb structure.

Embodiment 260

The method of any one of embodiments 223-259, wherein the washcoat layercomprising catalytically active particles has a thickness of 50 g/l to250 g/l.

Embodiment 261

The method of any one of embodiments 223-260, further comprisingdepositing a corner-fill layer directly on the substrate.

Embodiment 262

The method of any one of embodiments 223-261, wherein the coatedsubstrate has a platinum group metal loading of 4 g/l or less and alight-off temperature for carbon monoxide at least 5° C. lower than thelight-off temperature of a substrate with the same platinum group metalloading deposited by wet-chemistry methods.

Embodiment 263

The method of any one of embodiments 223-262, wherein the coatedsubstrate has a platinum group metal loading of about 1.0 g/l to about4.0 g/l.

Embodiment 264

The method of any one of embodiments 223-263, said coated substratehaving a platinum group metal loading of about 1.0 g/l to about 5.5 g/l,wherein after 125,000 miles of operation in a vehicular catalyticconverter, the coated substrate has a light-off temperature for carbonmonoxide at least 5° C. lower than a coated substrate prepared bydepositing platinum group metals by wet chemical methods having the sameplatinum group metal loading after 125,000 miles of operation in avehicular catalytic converter.

Embodiment 265

The method of any one of embodiments 223-264, said coated substratehaving a platinum group metal loading of about 1.0 g/l to about 5.5 g/l,wherein after aging for 16 hours at 800° C., the coated substrate has alight-off temperature for carbon monoxide at least 5° C. lower than acoated substrate prepared by depositing platinum group metals by wetchemical methods having the same platinum group metal loading afteraging for 16 hours at 800° C.

Embodiment 266

A method of forming a coated substrate comprising: coating a substratewith a washcoat composition comprising zeolite particles, a PNAmaterial, and catalytically active particles, wherein the catalyticallyactive particles comprise composite nano-particles bonded tomicron-sized carrier particles, and the composite nano-particlescomprise a support nano-particle and a catalytic nano-particle.

Embodiment 267

A method of forming a coated substrate, the method comprising: coating asubstrate with a washcoat composition comprising zeolite particles;coating the substrate with a washcoat composition comprising PNAmaterial according to any one of embodiments 42-71; and coating thesubstrate with a washcoat composition containing catalytically activeparticles.

Embodiment 268

The method of embodiment 267, further comprising coating the substratewith a corner-fill washcoat prior to coating the substrate with theother washcoats.

Embodiment 269

The method of any one of embodiments 267-268, wherein the washcoatcomposition comprising zeolite particles comprises a thickness of 25 g/lto 90 g/l.

Embodiment 270

The method of any one of embodiments 267-268, wherein the washcoatcomposition comprising catalytically active particles comprises athickness of 50 g/l to 250 g/l.

Embodiment 271

A coated substrate comprising a washcoat according to any one ofembodiments 42-71.

Embodiment 272

A coated substrate comprising a washcoat according to any one ofembodiments 42-71, further comprising a washcoat layer comprisingzeolite particles.

Embodiment 273

A catalytic converter comprising a coated substrate according toembodiment 270.

Embodiment 274

An exhaust treatment system comprising a conduit for exhaust gas and acatalytic converter according to embodiment 271.

Embodiment 275

A vehicle comprising a catalytic converter according to embodiment 271.

Embodiment 276

A diesel vehicle comprising a catalytic converter according toembodiment 271.

Embodiment 277

The diesel vehicle of embodiment 274, wherein the diesel vehicle is alight-duty diesel vehicle.

Embodiment 278

The vehicle of any one of embodiments 121, 170, and 275, wherein thevehicle complies with the European emission standard Euro 5.

Embodiment 279

The vehicle of any one of embodiments 121, 170, and 275, wherein thevehicle complies with the European emission standard Euro 6.

Embodiment 280

A vehicle comprising: a catalytic converter comprising between 1.0 g/land 4.0 g/l of platinum group metal; and a PNA material, wherein thevehicle complies with the European emission standard Euro 5.

Embodiment 281

The vehicle of embodiment 280, wherein the PNA material comprisesmanganese oxide on a plurality of micron-sized support particles.

Embodiment 282

The vehicle of any one of embodiments 280-281, wherein the PNA materialcomprises magnesium oxide on a plurality of micron-sized supportparticles.

Embodiment 283

The vehicle of any one of embodiments 280-282, wherein the PNA materialcomprises calcium oxide on a plurality of micron-sized supportparticles.

Embodiment 284

The vehicle of any one of embodiments 280-283, wherein the PNA materialcomprises manganese oxide, magnesium oxide, and calcium oxide ondifferent pluralities of micron-sized support particles.

Embodiment 285

The vehicle of any one of embodiments 281-284, wherein the manganeseoxide, magnesium oxide, and calcium oxide are nano-sized.

Embodiment 286

The vehicle of any one of embodiments 280-285, wherein the pluralitiesof support particles comprise ceria.

Embodiment 287

The vehicle of any one of embodiments 280 wherein the PNA materialcomprises about 150 g/L to about 350 g/L ceria.

Embodiment 288

The vehicle of any one of embodiments 286-287, wherein the PNA materialcomprises about 1% to about 20% manganese oxide by weight of the amountof ceria.

Embodiment 289

The vehicle of any one of embodiments 286-288, wherein the PNA materialcomprises about 1% to about 10% magnesium oxide by weight of the amountof ceria.

Embodiment 290

The vehicle of any one of embodiments 286-289, wherein the PNA materialcomprises about 1% to about 10% calcium oxide by weight of the amount ofceria.

Embodiment 291

The vehicle of any one of embodiments 286-290, wherein the PNA materialcomprises about 28 g/L manganese oxide.

Embodiment 292

The vehicle of any one of embodiments 286-291, wherein the PNA materialcomprises about 10.5 g/L magnesium oxide.

Embodiment 293

The vehicle of any one of embodiments 286-292, wherein the PNA materialcomprises about 10.5 g/L calcium oxide.

Embodiment 294

The vehicle of any one of embodiments 280-293, wherein the PNA materialstores NOx emissions from ambient temperature to about 100° C.

Embodiment 295

The vehicle of any one of embodiments 280-294, wherein the PNA materialstores NOx emissions from ambient temperature to about 150° C.

Embodiment 296

The vehicle of any one of embodiments 280-295, wherein the PNA materialstores NOx emissions from ambient temperature to about 200° C.

Embodiment 297

The vehicle of any one of embodiments 280-296, wherein the vehicle is adiesel vehicle.

Embodiment 298

The vehicle of any one of embodiments 280-297, wherein the dieselvehicle is a light-duty diesel vehicle.

Embodiment 299

The vehicle of any one of embodiments 280-298, wherein the vehiclecomplies with European emission standard Euro 6.

Embodiment 300

The vehicle of any one of embodiments 280-299, further comprising an SCRunit.

Embodiment 301

The vehicle of any one of embodiments 280-300, further comprising anLNT.

Embodiment 302

A catalytic converter comprising: a coated substrate comprising awashcoat layer comprising a PNA material.

Embodiment 303

The catalytic converter of embodiment 302, wherein the PNA materialcomprises manganese oxide on a plurality of micron-sized supportparticles.

Embodiment 304

The catalytic converter of any one of embodiments 302-303, wherein thePNA material comprises magnesium oxide on a plurality of micron-sizedsupport particles.

Embodiment 305

The catalytic converter of any one of embodiments 302-304, wherein thePNA material comprises calcium oxide on a plurality of micron-sizedsupport particles.

Embodiment 306

The catalytic converter of any one of embodiments 302-305, wherein thePNA material comprises manganese oxide, magnesium oxide, and calciumoxide on different pluralities of micron-sized support particles.

Embodiment 307

The catalytic converter of any one of embodiments 302-306, wherein themanganese oxide, magnesium oxide, and calcium oxide are nano-sized.

Embodiment 308

The catalytic converter of any one of embodiments 302-307, wherein thepluralities of support particles comprise ceria.

Embodiment 309

The catalytic converter of any one of embodiments 302-308, wherein thePNA material comprises about 150 g/L to about 350 g/L ceria.

Embodiment 310

The catalytic converter of any one of embodiments 302-309, wherein thePNA material comprises about 1% to about 20% manganese oxide by weightof the amount of ceria.

Embodiment 311

The catalytic converter of any one of embodiments 302-310, wherein thePNA material comprises about 1% to about 10% magnesium oxide by weightof the amount of ceria.

Embodiment 312

The catalytic converter of any one of embodiments 302-311, wherein thePNA material comprises about 1% to about 10% calcium oxide by weight ofthe amount of ceria.

Embodiment 313

The catalytic converter of any one of embodiments 302-312, wherein thePNA material comprises about 28 g/L manganese oxide.

Embodiment 314

The catalytic converter of any one of embodiments 302-313, wherein thePNA material comprises about 10.5 g/L magnesium oxide.

Embodiment 315

The catalytic converter of any one of embodiments 302-314, wherein thePNA material comprises about 10.5 g/L calcium oxide.

Embodiment 316

The catalytic converter of any one of embodiments 302-315, wherein thePNA material stores NOx emissions from ambient temperature to about 100°C.

Embodiment 317

The catalytic converter of any one of embodiments 302-316, wherein thePNA material stores NOx emissions from ambient temperature to about 150°C.

Embodiment 318

The catalytic converter of any one of embodiments 302-317, wherein thePNA material stores NOx emissions from ambient temperature to about 200°C.

Embodiment 319

An exhaust treatment system comprising a conduit for exhaust gas and acatalytic converter comprising a coated substrate comprising a washcoatlayer comprising a PNA material.

Embodiment 320

The exhaust treatment system of embodiment 319, wherein the PNA materialcomprises manganese oxide on a plurality of micron-sized supportparticles.

Embodiment 321

The exhaust treatment system of any one of embodiments 319-320, whereinthe PNA material comprises magnesium oxide on a plurality ofmicron-sized support particles.

Embodiment 322

The exhaust treatment system of any one of embodiments 319-321, whereinthe PNA material comprises calcium oxide on a plurality of micron-sizedsupport particles.

Embodiment 323

The exhaust treatment system of any one of embodiments 319-322, whereinthe PNA material comprises manganese oxide, magnesium oxide, and calciumoxide on different pluralities of micron-sized support particles.

Embodiment 324

The exhaust treatment system of any one of embodiments 319-323, whereinthe manganese oxide, magnesium oxide, and calcium oxide are nano-sized.

Embodiment 325

The exhaust treatment system of any one of embodiments 319-324, whereinthe pluralities of support particles comprise ceria.

Embodiment 326

The exhaust treatment system of any one of embodiments 319-325, whereinthe PNA material comprises about 150 g/L to about 350 g/L ceria.

Embodiment 327

The exhaust treatment system of any one of embodiments 319-326, whereinthe PNA material comprises about 1% to about 20% manganese oxide byweight of the amount of ceria.

Embodiment 328

The exhaust treatment system of any one of embodiments 319-327, whereinthe PNA material comprises about 1% to about 10% magnesium oxide byweight of the amount of ceria.

Embodiment 329

The exhaust treatment system of any one of embodiments 319-328, whereinthe PNA material comprises about 1% to about 10% calcium oxide by weightof the amount of ceria.

Embodiment 330

The exhaust treatment system of any one of embodiments 319-329, whereinthe PNA material comprises about 28 g/L manganese oxide.

Embodiment 331

The exhaust treatment system of any one of embodiments 319-330, whereinthe PNA material comprises about 10.5 g/L magnesium oxide.

Embodiment 332

The exhaust treatment system of any one of embodiments 319-331, whereinthe PNA material comprises about 10.5 g/L calcium oxide.

Embodiment 333

The exhaust treatment system of any one of embodiments 319-332, whereinthe PNA material stores NOx emissions from ambient temperature to about100° C.

Embodiment 334

The exhaust treatment system of any one of embodiments 319-333, whereinthe PNA material stores NOx emissions from ambient temperature to about150° C.

Embodiment 335

The exhaust treatment system of any one of embodiments 319-334, whereinthe PNA material stores NOx emissions from ambient temperature to about200° C.

Embodiment 336

The exhaust treatment system of any one of embodiments 319-335, furthercomprising an SCR unit.

Embodiment 337

The exhaust treatment system of any one of embodiments 319-336, furthercomprising an LNT.

Embodiment 338

A PNA material comprising: an alkali oxide or alkaline earth oxide on aplurality of micron-sized support particles.

Embodiment 339

The PNA material of embodiment 338, further comprising a second alkalioxide or alkaline earth oxide on a second plurality of micron-sizedsupport particles.

Embodiment 340

The PNA material of any one of embodiments 338-339, further comprising athird alkali oxide or alkaline earth oxide on a third plurality ofmicron-sized support particles.

Embodiment 341

The PNA material of any one of embodiments 338-340, wherein the first,second, and third alkali oxides or alkaline earth oxides are selectedfrom the group consisting of manganese oxide, magnesium oxide, andcalcium oxide.

Embodiment 342

The PNA material of any one of embodiments 338-341, further comprisingPGM.

Embodiment 343

The PNA material of embodiment 342, wherein PGM are on a fourthplurality of micron-sized support particles.

Embodiment 344

The PNA material of any one of embodiments 342-343, wherein PGM are onat least one of the first, second, or third pluralities of micron-sizedsupport particles.

Embodiment 345

The PNA material of any one of embodiments 342-344, wherein the PGMcomprises platinum, palladium, or a mixture thereof.

Embodiment 346

The PNA material of any one of embodiments 338-345, wherein the alkalioxides or alkaline earth oxides are nano-sized.

Embodiment 347

The PNA material of any one of embodiments 338-346, wherein thepluralities of support particles comprise ceria.

Embodiment 348

The PNA material of embodiment 347, wherein the PNA material comprisesabout 150 g/L to about 350 g/L ceria.

Embodiment 349

The PNA material of any one of embodiments 338-348, wherein the PNAmaterial stores NOx emissions from ambient temperature to about 100° C.

Embodiment 350

The PNA material of any one of embodiments 338-349, wherein the PNAmaterial stores NOx emissions from ambient temperature to about 150° C.

Embodiment 351

The PNA material of any one of embodiments 338-350, wherein the PNAmaterial stores NOx emissions from ambient temperature to about 200° C.

Embodiment 352

A PNA material comprising: a PGM on a plurality of micron-sized supportparticles.

Embodiment 353

The PNA material of embodiment 352, further comprising an alkali oxideor alkaline earth oxide on a second plurality of micron-sized supportparticles.

Embodiment 354

The PNA material of any one of embodiments 352-353, further comprising asecond alkali oxide or alkaline earth oxide on a third plurality ofmicron-sized support particles.

Embodiment 355

The PNA material of any one of embodiments 352-354, further comprising athird alkali oxide or alkaline earth oxide on a fourth plurality ofmicron-sized support particles.

Embodiment 356

The PNA material of any one of embodiments 352-355, wherein the first,second, and third alkali oxides or alkaline earth oxides are selectedfrom the group consisting of manganese oxide, magnesium oxide, andcalcium oxide.

Embodiment 357

The PNA material of any one of embodiments 352-356, wherein the alkalioxides or alkaline earth oxides are nano-sized.

Embodiment 358

The PNA material of any one of embodiments 352-357, further comprisingPGM on at least one of the first, second, or third pluralities ofmicron-sized support particles.

Embodiment 359

The PNA material of any one of embodiments 352-358, wherein PGM on aplurality of micron-sized support particles comprises a NNm particle.

Embodiment 360

The PNA material of any one of embodiments 352-359, wherein the PGM on aplurality of micron-sized support particles comprises a NNiM particle.

Embodiment 361

The PNA material of any one of embodiments 352-360, wherein the PGMcomprises platinum, palladium, or a mixture thereof.

Embodiment 362

The PNA material of any one of embodiments 352-361, wherein thepluralities of support particles comprise ceria.

Embodiment 363

The PNA material of embodiment 362, wherein the PNA material comprisesabout 150 g/L to about 350 g/L ceria.

Embodiment 364

The PNA material of any one of embodiments 352-363, wherein the PNAmaterial stores NOx emissions from ambient temperature to about 100° C.

Embodiment 365

The PNA material of any one of embodiments 352-364, wherein the PNAmaterial stores NOx emissions from ambient temperature to about 150° C.

Embodiment 366

The PNA material of any one of embodiments 352-365, wherein the PNAmaterial stores NOx emissions from ambient temperature to about 200° C.

Embodiment 367

A PNA material comprising: an alkali oxide or alkaline earth oxide andPGM on a plurality of micron-sized support particles.

Embodiment 368

The PNA material of embodiment 367, further comprising a second alkalioxide or alkaline earth oxide on a second plurality of micron-sizedsupport particles.

Embodiment 369

The PNA material of any one of embodiments 367-368, further comprising athird alkali oxide or alkaline earth oxide on a third plurality ofmicron-sized support particles.

Embodiment 370

The PNA material of any one of embodiments 367-369, wherein the first,second, and third alkali oxides or alkaline earth oxides are selectedfrom the group consisting of manganese oxide, magnesium oxide, andcalcium oxide.

Embodiment 371

The PNA material of any one of embodiments 367-370, wherein PGM are on afourth plurality of micron-sized support particles.

Embodiment 372

The PNA material of any one of embodiments 367-371, wherein the PGMcomprises platinum, palladium, or a mixture thereof.

Embodiment 373

The PNA material of any one of embodiments 367-372, wherein the alkalioxides or alkaline earth oxides are nano-sized.

Embodiment 374

The PNA material of any one of embodiments 367-373, wherein thepluralities of support particles comprise ceria.

Embodiment 375

The PNA material of embodiment 374, wherein the PNA material comprisesabout 150 g/L to about 350 g/L ceria.

Embodiment 376

The PNA material of any one of embodiments 367-375, wherein the PNAmaterial stores NOx emissions from ambient temperature to about 100° C.

Embodiment 377

The PNA material of any one of embodiments 367-376, wherein the PNAmaterial stores NOx emissions from ambient temperature to about 150° C.

Embodiment 378

The PNA material of any one of embodiments 367-377, wherein the PNAmaterial stores NOx emissions from ambient temperature to about 200° C.

Embodiment 379

A method of forming a PNA material comprising: applying a first alkalioxide or alkaline earth oxide to a first plurality of micron-sizedsupport particles; applying a second alkali oxide or alkaline earthoxide to a second plurality of micron-sized support particles; andcombining the first and second pluralities of micron-sized supportparticles.

Embodiment 380

The method of embodiment 379, further comprising applying a third alkalioxide or alkaline earth oxide to a third plurality of micron-sizedsupport particles and combining the third plurality of micron-sizedsupport particles with the first and second pluralities of micron-sizedsupport particles.

Embodiment 381

The method of any one of embodiments 379-380, wherein the first, second,and third alkali oxides or alkaline earth oxides are selected from thegroup consisting of manganese oxide, magnesium oxide, and calcium oxide.

Embodiment 382

The method of any one of embodiments 379-381, further comprisingapplying PGM to a fourth plurality of micron-sized support particles andcombining the fourth plurality of micron-sized support particles withthe first and second pluralities of micron-sized support particles.

Embodiment 383

The method of any one of embodiments 379-382, further comprisingapplying PGM to at least one of the first, second, or third pluralitiesof micron-sized support particles.

Embodiment 384

The method of any one of embodiments 382-383, wherein the PGM comprisesplatinum, palladium, or a mixture thereof.

Embodiment 385

The method of any one of embodiments 379-384, wherein the alkali oxidesor alkaline earth oxides are nano-sized.

Embodiment 386

The method of any one of embodiments 379-385, wherein the pluralities ofsupport particles comprise ceria.

Embodiment 387

The method of embodiment 386, wherein the PNA material comprises about150 g/L to about 350 g/L ceria.

Embodiment 388

The method of any one of embodiments 379-387, wherein the PNA materialstores NOx emissions from ambient temperature to about 100° C.

Embodiment 389

The method of any one of embodiments 379-388, wherein the PNA materialstores NOx emissions from ambient temperature to about 150° C.

Embodiment 390

The method of any one of embodiments 379-389, wherein the PNA materialstores NOx emissions from ambient temperature to about 200° C.

Embodiment 391

A method of forming a PNA material comprising: applying alkali oxide oralkaline earth oxide to a first plurality of micron-sized supportparticles; applying PGM to a second plurality of micron-sized supportparticles; and combining the first and second pluralities ofmicron-sized support particles.

Embodiment 392

The method of embodiment 391 further comprising applying a second alkalioxide or alkaline earth oxide on a third plurality of micron-sizedsupport particles and combining the third plurality of micron-sizedsupport particles with the first and second pluralities of micron-sizedsupport particles.

Embodiment 393

The method of anyone of embodiments 391-392, further comprising applyinga third alkali oxide or alkaline earth oxide on a fourth plurality ofmicron-sized support particles and combining the fourth plurality ofmicron-sized support particles with the first and second pluralities ofmicron-sized support particles.

Embodiment 394

The method of any one of embodiments 391-393, wherein the first, second,and third alkali oxides or alkaline earth oxides are selected from thegroup consisting of manganese oxide, magnesium oxide, and calcium oxide.

Embodiment 395

The method of any one of embodiments 391-394, wherein the alkali oxidesor alkaline earth oxides are nano-sized.

Embodiment 396

The method of any one of embodiments 391-395, further comprisingapplying PGM to at least one of the first, second, or third pluralitiesof micron-sized support particles.

Embodiment 397

The method of any one of embodiments 391-396, wherein the PGM on aplurality of micron-sized support particles comprises a NNm particle.

Embodiment 398

The method of any one of embodiments 391-397, wherein the PGM on aplurality of micron-sized support particles comprises a NNiM particle.

Embodiment 399

The method of any one of embodiments 391-398, wherein the PGM comprisesplatinum, palladium, or a mixture thereof.

Embodiment 400

The method of any one of embodiments 391-399, wherein the pluralities ofsupport particles comprise ceria.

Embodiment 401

The method of embodiment 400, wherein the PNA material comprises about150 g/L to about 350 g/L ceria.

Embodiment 402

The method of any one of embodiments 391-401, wherein the PNA materialstores NOx emissions from ambient temperature to about 100° C.

Embodiment 403

The method of any one of embodiments 391-402, wherein the PNA materialstores NOx emissions from ambient temperature to about 150° C.

Embodiment 404

The method of any one of embodiments 391-403, wherein the PNA materialstores NOx emissions from ambient temperature to about 200° C.

Embodiment 405

A method of forming a PNA material comprising: applying alkali oxide oralkaline earth oxide to a plurality of micron-sized support particles;and applying PGM to the plurality of micron sized support particles.

Embodiment 406

The method of embodiment 405, further comprising applying a secondalkali oxide or alkaline earth oxide on a second plurality ofmicron-sized support particles and combining the first plurality ofmicron-sized support particles with the second plurality of micron-sizedsupport particles.

Embodiment 407

The method of anyone of embodiments 405-406, further comprising applyinga third alkali oxide or alkaline earth oxide on a third plurality ofmicron-sized support particles and combining the third plurality ofmicron-sized support particles with the first plurality of micron-sizedsupport particles.

Embodiment 408

The method of any one of embodiments 405-407, wherein the first, second,and third alkali oxides or alkaline earth oxides are selected from thegroup consisting of manganese oxide, magnesium oxide, and calcium oxide.

Embodiment 409

The method of any one of embodiments 405-408, further comprisingapplying PGM to a fourth plurality of micron-sized support particles andcombining the fourth plurality of micron-sized support particles withthe first plurality of micron-sized support particles.

Embodiment 410

The method of any one of embodiments 405-409, wherein the PGM comprisesplatinum, palladium, or a mixture thereof.

Embodiment 411

The method of any one of embodiments 405-410, wherein the alkali oxidesor alkaline earth oxides are nano-sized.

Embodiment 412

The method of any one of embodiments 405-411, wherein the pluralities ofsupport particles comprise ceria.

Embodiment 413

The method of embodiment 412, wherein the PNA material comprises about150 g/L to about 350 g/L ceria.

Embodiment 414

The method of any one of embodiments 405-413, wherein the PNA materialstores NOx emissions from ambient temperature to about 100° C.

Embodiment 415

The method of any one of embodiments 405-414, wherein the PNA materialstores NOx emissions from ambient temperature to about 150° C.

Embodiment 416

The method of any one of embodiments 405-415, wherein the PNA materialstores NOx emissions from ambient temperature to about 200° C.

Embodiment 417

A washcoat composition comprising a solids content of: 95% to 98% byweight PNA material; and 2% to 5% by weight of boehmite particles.

Embodiment 418

The washcoat composition of embodiment 417, wherein the PNA materialcomprises an alkali oxide or alkaline earth oxide on a plurality ofmicron-sized support particles.

Embodiment 419

The washcoat composition of any one of embodiments 417-418, wherein thePNA material comprises a second alkali oxide or alkaline earth oxide ona second plurality of micron-sized support particles.

Embodiment 420

The washcoat composition of any one of embodiments 417-419, wherein thePNA material comprises a third alkali oxide or alkaline earth oxide on athird plurality of micron-sized support particles.

Embodiment 421

The washcoat composition of any one of embodiments 417-420, wherein thefirst, second, and third alkali oxides or alkaline earth oxides areselected from the group consisting of manganese oxide, magnesium oxide,and calcium oxide.

Embodiment 422

The washcoat composition of any one of embodiments 417-421, wherein thePNA material comprises PGM.

Embodiment 423

The washcoat composition of embodiment 422, wherein PGM are on a fourthplurality of micron-sized support particles.

Embodiment 424

The washcoat composition of any one of embodiments 422-423, wherein PGMare on at least one of the first, second, or third pluralities ofmicron-sized support particles.

Embodiment 425

The washcoat composition of any one of embodiments 422-424, wherein thePGM comprises platinum, palladium, or a mixture thereof.

Embodiment 426

The washcoat composition of any one of embodiments 422-2425, wherein thePGM on a plurality of micron-sized support particles comprises a NNm orNNiM particle.

Embodiment 427

The washcoat composition of any one of embodiments 417-426, wherein thealkali oxides or alkaline earth oxides are nano-sized.

Embodiment 428

The washcoat composition of any one of embodiments 417-427, wherein thepluralities of support particles comprise ceria.

Embodiment 429

The washcoat composition of embodiment 428, wherein the PNA materialcomprises about 150 g/L to about 350 g/L ceria.

Embodiment 430

The washcoat composition of any one of embodiments 417-429, wherein thePNA material stores NOx emissions from ambient temperature to about 100°C.

Embodiment 431

The washcoat composition of any one of embodiments 417-430, wherein thePNA material stores NOx emissions from ambient temperature to about 150°C.

Embodiment 432

The washcoat composition of any one of embodiments 417-431, wherein thePNA material stores NOx emissions from ambient temperature to about 200°C.

Embodiment 433

The washcoat composition of any one of embodiments 417-432, wherein thesolids are suspended in an aqueous medium at a pH between 3 and 5.

Embodiment 434

A coated substrate comprising: a substrate; a washcoat layer comprisingzeolite particles; a washcoat layer comprising PNA material; and awashcoat layer comprising catalytically active particles, wherein thecatalytically active particles comprise composite nano-particles bondedto micron-sized carrier particles, and the composite nano-particlescomprise a support nano-particle and a catalytic nano-particle.

Embodiment 435

The coated substrate of embodiment 434, wherein the washcoat layercomprising PNA material is formed on top of the washcoat layercomprising catalytically active particles.

Embodiment 436

The coated substrate of any one of embodiments 434-435, wherein thewashcoat layer comprising catalytically active particles is formed ontop of the washcoat layer comprising PNA material.

Embodiment 437

The coated substrate of any one of embodiments 434-436, wherein thewashcoat layer comprising zeolite particles is formed on top of thewashcoat layer comprising PNA material.

Embodiment 438

The coated substrate of any one of embodiments 434-437, wherein thewashcoat layer comprising PNA material is formed on top of the washcoatlayer comprising zeolite particles.

Embodiment 439

The coated substrate of any one of embodiments 434-438, wherein thewashcoat layer comprising catalytically active particles is formed ontop of the washcoat layer comprising zeolite particles.

Embodiment 440

The coated substrate of any one of embodiments 434-439, wherein thewashcoat layer comprising zeolite particles is formed on top of thewashcoat layer comprising catalytically active particles.

Embodiment 441

The coated substrate of any one of embodiments 434-440, wherein the PNAmaterial comprises an alkali oxide or alkaline earth oxide on aplurality of micron-sized support particles.

Embodiment 442

The coated substrate of any one of embodiments 434-441, wherein the PNAmaterial comprises a second alkali oxide or alkaline earth oxide on asecond plurality of micron-sized support particles.

Embodiment 443

The coated substrate of any one of embodiments 434-442 wherein the PNAmaterial comprises a third alkali oxide or alkaline earth oxide on athird plurality of micron-sized support particles.

Embodiment 444

The coated substrate of any one of embodiments 434-443, wherein thefirst, second, and third alkali oxides or alkaline earth oxides areselected from the group consisting of manganese oxide, magnesium oxide,and calcium oxide.

Embodiment 445

The coated substrate of any one of embodiments 434-444, wherein the PNAmaterial comprises PGM.

Embodiment 446

The coated substrate of embodiment 445, wherein PGM are on a fourthplurality of micron-sized support particles.

Embodiment 447

The coated substrate of any one of embodiments 445-446, wherein PGM areon at least one of the first, second, or third pluralities ofmicron-sized support particles.

Embodiment 448

The coated substrate of any one of embodiments 445-447, wherein the PGMcomprises platinum, palladium, or a mixture thereof.

Embodiment 449

The coated substrate of any one of embodiments 445-448, wherein the PGMon a plurality of micron-sized support particles comprises a NNm or NNiMparticle.

Embodiment 450

The coated substrate of any one of embodiments 434-449, wherein thealkali oxides or alkaline earth oxides are nano-sized.

Embodiment 451

The coated substrate of any one of embodiments 434-450, wherein thepluralities of support particles comprise ceria.

Embodiment 452

The coated substrate of embodiment 451, wherein the PNA materialcomprises about 150 g/L to about 350 g/L ceria.

Embodiment 453

The coated substrate of any one of embodiments 434-452, wherein the PNAmaterial stores NOx emissions from ambient temperature to about 100° C.

Embodiment 454

The coated substrate of any one of embodiments 434-453, wherein the PNAmaterial stores NOx emissions from ambient temperature to about 150° C.

Embodiment 455

The coated substrate of any one of embodiments 434-454, wherein the PNAmaterial stores NOx emissions from ambient temperature to about 200° C.

Embodiment 456

The coated substrate of any one of embodiments 434-455, wherein thewashcoat layer comprising the PNA material further comprises boehmiteparticles.

Embodiment 457

The coated substrate of any one of embodiments 434-456, wherein the PNAmaterial comprises 95% to 98% by weight of the mixture of PNA materialand boehmite particles in the washcoat layer comprising PNA material.

Embodiment 458

The coated substrate of any one of embodiments 434-457, wherein theboehmite particles comprise 2% to 5% by weight of the mixture of PNAmaterial and boehmite particles in the washcoat layer comprising PNAmaterial.

Embodiment 459

The coated substrate of any one of embodiments 434-458, wherein thecatalytic nano-particles comprise at least one platinum group metal.

Embodiment 460

The coated substrate of any one of embodiments 434-459, wherein thecatalytic nano-particles comprise platinum and palladium.

Embodiment 461

The coated substrate of any one of embodiments 434-460, wherein thecatalytic nano-particles comprise platinum and palladium in a weightratio of 2:1 platinum:palladium

Embodiment 462

The coated substrate of any one of embodiments 434-461, wherein thesupport nano-particles have an average diameter of 10 nm to 20 nm.

Embodiment 463

The coated substrate of any one of embodiments 434-462, wherein thecatalytic nano-particles have an average diameter of between 1 nm and 5nm.

Embodiment 464

The coated substrate of any one of embodiments 434-463, wherein thewashcoat layer comprising zeolite particles comprises metal-oxideparticles and boehmite particles.

Embodiment 465

The coated substrate of any one of embodiments 434-464, wherein themetal-oxide particles are aluminum-oxide particles.

Embodiment 466

The coated substrate of any one of embodiments 434-465, wherein thezeolite particles comprise 60% to 80% by weight of the mixture ofzeolite particles, metal-oxide particles, and boehmite particles in thewashcoat layer comprising zeolite particles.

Embodiment 467

The coated substrate of any one of embodiments 434-466, wherein theboehmite particles comprise 2% to 5% by weight of the mixture of zeoliteparticles, metal-oxide particles, and boehmite particles in the washcoatlayer comprising zeolite particles.

Embodiment 468

The coated substrate of embodiments 434-167, wherein the metal-oxideparticles comprise 15% to 38% by weight of the mixture of zeoliteparticles, metal-oxide particles, and boehmite particles in the washcoatlayer comprising zeolite particles.

Embodiment 469

The coated substrate of any one of embodiments 434-468, wherein thewashcoat layer comprising zeolite particles does not include platinumgroup metals.

Embodiment 470

The coated substrate of any one of embodiments 434-469, wherein thezeolite particles in the washcoat layer comprising zeolite particleseach have a diameter of 0.2 microns to 8 microns.

Embodiment 471

The coated substrate of any one of embodiments 434-470, wherein thewashcoat layer comprising catalytically active particles furthercomprises boehmite particles and silica particles.

Embodiment 472

The coated substrate of any one of embodiments 434-471, wherein thewashcoat layer comprising catalytically active particles issubstantially free of zeolites

Embodiment 473

The coated substrate of any one of embodiments 434-472, wherein thecatalytically active particles comprise 35% to 95% by weight of thecombination of the catalytically active particles, boehmite particles,and silica particles in the washcoat layer comprising catalyticallyactive particles.

Embodiment 474

The coated substrate of any one of embodiments 434-473, wherein thesilica particles are present in an amount up to 20% by weight of thecombination of the catalytically active particles, boehmite particles,and silica particles in the washcoat layer comprising catalyticallyactive particles

Embodiment 475

The coated substrate of any one of embodiments 434-474, wherein theboehmite particles comprise 2% to 5% by weight of the combination of thecatalytically active particles, the boehmite particles, and the silicaparticles in the washcoat layer comprising catalytically activeparticles

Embodiment 476

The coated substrate of any one of embodiments 434-475, wherein thewashcoat layer comprising catalytically active particles comprises 92%by weight of the catalytically active particles, 3% by weight of theboehmite particles, and 5% by weight of the silica particles

Embodiment 477

The coated substrate of any one of embodiments 434-476, wherein thesubstrate comprises cordierite.

Embodiment 478

The coated substrate of any one of embodiments 434-477, wherein thesubstrate comprises a honeycomb structure.

Embodiment 479

The coated substrate of any one of embodiments 434-478, wherein thewashcoat layer comprising zeolite particles has a thickness of 25 g/l to90 g/l.

Embodiment 480

The coated substrate of any one of embodiments 434-479, wherein thewashcoat layer comprising catalytically active particles has a thicknessof 50 g/l to 250 g/l.

Embodiment 481

The coated substrate of any one of embodiments 434-480, furthercomprising a corner-fill layer deposited directly on the substrate.

Embodiment 482

The coated substrate of any one of embodiments 434-481, wherein thecoated substrate has a platinum group metal loading of 4 g/l or less anda light-off temperature for carbon monoxide at least 5° C. lower thanthe light-off temperature of a substrate with the same platinum groupmetal loading deposited by wet-chemistry methods.

Embodiment 483

The coated substrate of any one of embodiments 434-482, wherein thecoated substrate has a platinum group metal loading of about 1.0 g/l toabout 4.0 g/l.

Embodiment 484

The coated substrate of any one of embodiments 434-483, said coatedsubstrate having a platinum group metal loading of about 1.0 g/l toabout 5.5 g/l, wherein after 125,000 miles of operation in a vehicularcatalytic converter, the coated substrate has a light-off temperaturefor carbon monoxide at least 5° C. lower than a coated substrateprepared by depositing platinum group metals by wet chemical methodshaving the same platinum group metal loading after 125,000 miles ofoperation in a vehicular catalytic converter.

Embodiment 485

The coated substrate of any one of embodiments 434-484, said coatedsubstrate having a platinum group metal loading of about 1.0 g/l toabout 5.5 g/l, wherein after aging for 16 hours at 800° C., the coatedsubstrate has a light-off temperature for carbon monoxide at least 5° C.lower than a coated substrate prepared by depositing platinum groupmetals by wet chemical methods having the same platinum group metalloading after aging for 16 hours at 800° C.

Embodiment 486

A catalytic converter comprising a coated substrate of any one ofembodiments 434-485.

Embodiment 487

An exhaust treatment system comprising a conduit for exhaust gas and acatalytic converter according to embodiment 486.

Embodiment 488

A vehicle comprising a catalytic converter according to embodiment 486.

Embodiment 489

A diesel vehicle comprising a catalytic converter according toembodiment 486.

Embodiment 490

The diesel vehicle of embodiment 489, wherein the diesel vehicle is alight-duty diesel vehicle.

Embodiment 491

A method of treating an exhaust gas, comprising contacting the coatedsubstrate of any one of embodiments 434-485 with the exhaust gas.

Embodiment 492

A method of treating an exhaust gas, comprising contacting the coatedsubstrate of any one of embodiments 434-485 with the exhaust gas,wherein the substrate is housed within a catalytic converter configuredto receive the exhaust gas.

Embodiment 493

A method of forming a coated substrate comprising: coating a substratewith a washcoat composition comprising zeolite particles; coating thesubstrate with a washcoat composition comprising a PNA material; andcoating the substrate with a washcoat composition comprisingcatalytically active particles, wherein the catalytically activeparticles comprise composite nano-particles bonded to micron-sizedcarrier particles, and the composite nano-particles comprise a supportnano-particle and a catalytic nano-particle.

Embodiment 494

The method of embodiment 493, wherein coating the substrate with thewashcoat layer comprising PNA material is performed before coating thesubstrate with the washcoat comprising catalytically active particles.

Embodiment 495

The method of any one of embodiments 493-494, wherein coating thesubstrate with the washcoat layer comprising catalytically activeparticles is performed before coating the substrate with the washcoatlayer comprising PNA material.

Embodiment 496

The method of any one of embodiments 493-495, wherein coating thesubstrate with the washcoat layer comprising zeolite particles isperformed before coating the substrate with the washcoat layercomprising PNA material.

Embodiment 497

The method of any one of embodiments 493-496, wherein coating thesubstrate with the washcoat layer comprising PNA material is performedbefore coating the substrate with the washcoat layer comprising zeoliteparticles.

Embodiment 498

The method of any one of embodiments 493-497, wherein coating thesubstrate with the washcoat layer comprising catalytically activeparticles is performed before coating the substrate with the washcoatlayer comprising zeolite particles.

Embodiment 499

The method of any one of embodiments 493-498, wherein coating thesubstrate with the washcoat layer comprising zeolite particles isperformed before coating the substrate with the washcoat layercomprising catalytically active particles.

Embodiment 500

The method of any one of embodiments 493-499, wherein the PNA materialcomprises an alkali oxide or alkaline earth oxide on a plurality ofmicron-sized support particles.

Embodiment 501

The method of any one of embodiments 493-500, wherein the PNA materialcomprises a second alkali oxide or alkaline earth oxide on a secondplurality of micron-sized support particles.

Embodiment 502

The method of any one of embodiments 493-501, wherein the PNA materialcomprises a third alkali oxide or alkaline earth oxide on a thirdplurality of micron-sized support particles.

Embodiment 503

The method of any one of embodiments 493-502, wherein the first, second,and third alkali oxides or alkaline earth oxides are selected from thegroup consisting of manganese oxide, magnesium oxide, and calcium oxide.

Embodiment 504

The method of any one of embodiments 493-503, wherein the PNA materialcomprises PGM.

Embodiment 505

The method of embodiment 504, wherein PGM are on a fourth plurality ofmicron-sized support particles.

Embodiment 506

The method of any one of embodiments 504-505, wherein PGM are on atleast one of the first, second, or third pluralities of micron-sizedsupport particles.

Embodiment 507

The method of any one of embodiments 504-506, wherein the PGM comprisesplatinum, palladium, or a mixture thereof.

Embodiment 508

The method of any one of embodiments 504-507, wherein the PGM on aplurality of micron-sized support particles comprises a NNm or NNiMparticle.

Embodiment 509

The method of any one of embodiments 493-508, wherein the alkali oxidesor alkaline earth oxides are nano-sized.

Embodiment 510

The method of any one of embodiments 493-509, wherein the pluralities ofsupport particles comprise ceria.

Embodiment 511

The method of embodiment 510, wherein the PNA material comprises about150 g/L to about 350 g/L ceria.

Embodiment 512

The method of any one of embodiments 493-511 wherein the PNA materialstores NOx emissions from ambient temperature to about 100° C.

Embodiment 513

The method of any one of embodiments 493-512, wherein the PNA materialstores NOx emissions from ambient temperature to about 150° C.

Embodiment 514

The method of any one of embodiments 493-513, wherein the PNA materialstores NOx emissions from ambient temperature to about 200° C.

Embodiment 515

The method of any one of embodiments 493-514, wherein the washcoat layercomprising the PNA material further comprises boehmite particles.

Embodiment 516

The method of any one of embodiments 493-515, wherein the PNA materialcomprises 95% to 98% by weight of the mixture of PNA material andboehmite particles in the washcoat layer comprising PNA material.

Embodiment 517

The method of any one of embodiments 493-516, wherein the boehmiteparticles comprise 2% to 5% by weight of the mixture of PNA material andboehmite particles in the washcoat layer comprising PNA material.

Embodiment 518

The method of any one of embodiments 493-517, wherein the catalyticnano-particles comprise at least one platinum group metal.

Embodiment 519

The method of any one of embodiments 493-518, wherein the catalyticnano-particles comprise platinum and palladium.

Embodiment 520

The method of any one of embodiments 493-519, wherein the catalyticnano-particles comprise platinum and palladium in a weight ratio of 2:1platinum:palladium

Embodiment 521

The method of any one of embodiments 493-520, wherein the supportnano-particles have an average diameter of 10 nm to 20 nm.

Embodiment 522

The method of any one of embodiments 493-521, wherein the catalyticnano-particles have an average diameter of between 1 nm and 5 nm.

Embodiment 523

The method of any one of embodiments 493-522, wherein the washcoat layercomprising zeolite particles comprises metal-oxide particles andboehmite particles.

Embodiment 524

The method of any one of embodiments 493-523, wherein the metal-oxideparticles are aluminum-oxide particles.

Embodiment 525

The method of any one of embodiments 493-524, wherein the zeoliteparticles comprise 60% to 80% by weight of the mixture of zeoliteparticles, metal-oxide particles, and boehmite particles in the washcoatlayer comprising zeolite particles.

Embodiment 526

The method of any one of embodiments 493-525, wherein the boehmiteparticles comprise 2% to 5% by weight of the mixture of zeoliteparticles, metal-oxide particles, and boehmite particles in the washcoatlayer comprising zeolite particles.

Embodiment 527

The method of embodiments 493-526, wherein the metal-oxide particlescomprise 15% to 38% by weight of the mixture of zeolite particles,metal-oxide particles, and boehmite particles in the washcoat layercomprising zeolite particles.

Embodiment 528

The method of any one of embodiments 493-527, wherein the washcoat layercomprising zeolite particles does not include platinum group metals.

Embodiment 529

The method of any one of embodiments 493-528, wherein the zeoliteparticles in the washcoat layer comprising zeolite particles each have adiameter of 0.2 microns to 8 microns.

Embodiment 530

The method of any one of embodiments 493-529, wherein the washcoat layercomprising catalytically active particles further comprises boehmiteparticles and silica particles.

Embodiment 531

The method of any one of embodiments 493-530, wherein the washcoat layercomprising catalytically active particles is substantially free ofzeolites

Embodiment 532

The method of any one of embodiments 493-531, wherein the catalyticallyactive particles comprise 35% to 95% by weight of the combination of thecatalytically active particles, boehmite particles, and silica particlesin the washcoat layer comprising catalytically active particles.

Embodiment 533

The method of any one of embodiments 493-532, wherein the silicaparticles are present in an amount up to 20% by weight of thecombination of the catalytically active particles, boehmite particles,and silica particles in the washcoat layer comprising catalyticallyactive particles

Embodiment 534

The method of any one of embodiments 493-533, wherein the boehmiteparticles comprise 2% to 5% by weight of the combination of thecatalytically active particles, the boehmite particles, and the silicaparticles in the washcoat layer comprising catalytically activeparticles

Embodiment 535

The method of any one of embodiments 493-534, wherein the washcoat layercomprising catalytically active particles comprises 92% by weight of thecatalytically active particles, 3% by weight of the boehmite particles,and 5% by weight of the silica particles

Embodiment 536

The method of any one of embodiments 493-535, wherein the substratecomprises cordierite.

Embodiment 537

The method of any one of embodiments 493-536, wherein the substratecomprises a honeycomb structure.

Embodiment 538

The method of any one of embodiments 493-537, wherein the washcoat layercomprising zeolite particles has a thickness of 25 g/l to 90 g/l.

Embodiment 539

The method of any one of embodiments 493-538, wherein the washcoat layercomprising catalytically active particles has a thickness of 50 g/l to250 g/l.

Embodiment 540

The method of any one of embodiments 493-539, further comprising coatingthe substrate with a corner-fill washcoat prior to coating the substratewith the other washcoats.

Embodiment 541

The method of any one of embodiments 493-540, wherein the coatedsubstrate has a platinum group metal loading of 4 g/l or less and alight-off temperature for carbon monoxide at least 5° C. lower than thelight-off temperature of a substrate with the same platinum group metalloading deposited by wet-chemistry methods.

Embodiment 542

The method of any one of embodiments 493-541, wherein the coatedsubstrate has a platinum group metal loading of about 1.0 g/l to about4.0 g/l.

Embodiment 543

The method of any one of embodiments 493-542, said coated substratehaving a platinum group metal loading of about 1.0 g/l to about 5.5 g/l,wherein after 125,000 miles of operation in a vehicular catalyticconverter, the coated substrate has a light-off temperature for carbonmonoxide at least 5° C. lower than a coated substrate prepared bydepositing platinum group metals by wet chemical methods having the sameplatinum group metal loading after 125,000 miles of operation in avehicular catalytic converter.

Embodiment 544

The method of any one of embodiments 493-543, said coated substratehaving a platinum group metal loading of about 1.0 g/l to about 5.5 g/l,wherein after aging for 16 hours at 800° C., the coated substrate has alight-off temperature for carbon monoxide at least 5° C. lower than acoated substrate prepared by depositing platinum group metals by wetchemical methods having the same platinum group metal loading afteraging for 16 hours at 800° C.

Embodiment 545

A method of forming a coated substrate, the method comprising: coating asubstrate with a washcoat composition comprising zeolite particles;coating the substrate with a washcoat composition comprising PNAmaterial according to any one of embodiments 417-433; and coating thesubstrate with a washcoat composition containing catalytically activeparticles.

Embodiment 546

The method of embodiment 545, wherein coating the substrate with thewashcoat layer comprising PNA material is performed before coating thesubstrate with the washcoat comprising catalytically active particles.

Embodiment 547

The method of any one of embodiments 545-546, wherein coating thesubstrate with the washcoat layer comprising catalytically activeparticles is performed before coating the substrate with the washcoatlayer comprising PNA material.

Embodiment 548

The method of any one of embodiments 545-547, wherein coating thesubstrate with the washcoat layer comprising zeolite particles isperformed before coating the substrate with the washcoat layercomprising PNA material.

Embodiment 549

The method of any one of embodiments 545-548, wherein coating thesubstrate with the washcoat layer comprising PNA material is performedbefore coating the substrate with the washcoat layer comprising zeoliteparticles.

Embodiment 550

The method of any one of embodiments 545-549, wherein coating thesubstrate with the washcoat layer comprising catalytically activeparticles is performed before coating the substrate with the washcoatlayer comprising zeolite particles.

Embodiment 551

The method of any one of embodiments 545-550, wherein coating thesubstrate with the washcoat layer comprising zeolite particles isperformed before coating the substrate with the washcoat layercomprising catalytically active particles.

Embodiment 552

The method of any one of embodiments 545-551, further comprising coatingthe substrate with a corner-fill washcoat prior to coating the substratewith the other washcoats.

Embodiment 553

The method of any one of embodiments 545-552, wherein the washcoatcomposition comprising zeolite particles comprises a thickness of 25 g/lto 90 g/l.

Embodiment 554

The method of any one of embodiments 545-553 wherein the washcoatcomposition comprising catalytically active particles comprises athickness of 50 g/l to 250 g/l.

Embodiment 555

A catalytic converter comprising a coated substrate according to any oneof embodiments 545-554.

Embodiment 556

An exhaust treatment system comprising a conduit for exhaust gas and acatalytic converter according to embodiment 555.

Embodiment 557

A vehicle comprising a catalytic converter according to embodiment 555.

Embodiment 558

A diesel vehicle comprising a catalytic converter according toembodiment 555.

Embodiment 559

The diesel vehicle of embodiment 558, wherein the diesel vehicle is alight-duty diesel vehicle.

Embodiment 560

A coated substrate comprising a washcoat composition according toembodiments 417-433.

Embodiment 561

The vehicle of any one of embodiments 488 and 557, wherein the vehiclecomplies with the European emission standard Euro 5.

Embodiment 562

The vehicle of any one of embodiments 488 and 557, wherein the vehiclecomplies with the European emission standard Euro 6.

Embodiment 563

A vehicle comprising: a catalytic converter comprising between 1.0 g/land 4.0 g/l of platinum group metal; and a PNA material, wherein thevehicle complies with the European emission standard Euro 5.

Embodiment 564

The vehicle of embodiment 563, wherein the PNA material comprises analkali oxide or alkaline earth oxide on a plurality of micron-sizedsupport particles.

Embodiment 565

The vehicle of any one of embodiments 563-564, wherein the PNA materialcomprises a second alkali oxide or alkaline earth oxide on a secondplurality of micron-sized support particles.

Embodiment 566

The vehicle of any one of embodiments 563-565, wherein the PNA materialcomprises a third alkali oxide or alkaline earth oxide on a thirdplurality of micron-sized support particles.

Embodiment 567

The vehicle of any one of embodiments 563-566, wherein the first,second, and third alkali oxides or alkaline earth oxides are selectedfrom the group consisting of manganese oxide, magnesium oxide, andcalcium oxide.

Embodiment 568

The vehicle of any one of embodiments 563-567, wherein the PNA materialcomprises PGM.

Embodiment 569

The vehicle of embodiment 568, wherein PGM are on a fourth plurality ofmicron-sized support particles.

Embodiment 570

The vehicle of any one of embodiments 568-569, wherein PGM are on atleast one of the first, second, or third pluralities of micron-sizedsupport particles.

Embodiment 571

The vehicle of any one of embodiments 568-570, wherein the PGM comprisesplatinum, palladium, or a mixture thereof.

Embodiment 572

The vehicle of any one of embodiments 568-571, wherein the PGM on aplurality of micron-sized support particles comprises a NNm or NNiMparticle.

Embodiment 573

The vehicle of any one of embodiments 563-572, wherein the alkali oxidesor alkaline earth oxides are nano-sized.

Embodiment 574

The vehicle of any one of embodiments 563-573, wherein the pluralitiesof support particles comprise ceria.

Embodiment 575

The vehicle of embodiment 574, wherein the PNA material comprises about150 g/L to about 350 g/L ceria.

Embodiment 576

The vehicle of any one of embodiments 563-575, wherein the PNA materialstores NOx emissions from ambient temperature to about 100° C.

Embodiment 577

The vehicle of any one of embodiments 563-576, wherein the PNA materialstores NOx emissions from ambient temperature to about 150° C.

Embodiment 578

The vehicle of any one of embodiments 563-577, wherein the PNA materialstores NOx emissions from ambient temperature to about 200° C.

Embodiment 579

The vehicle of any one of embodiments 563-578, wherein the vehicle is adiesel vehicle.

Embodiment 580

The vehicle of any one of embodiments 563-579, wherein the dieselvehicle is a light-duty diesel vehicle.

Embodiment 581

The vehicle of any one of embodiments 563-580, wherein the vehiclecomplies with European emission standard Euro 6.

Embodiment 582

The vehicle of any one of embodiments 563-581, further comprising an SCRunit.

Embodiment 583

The vehicle of any one of embodiments 563-582, further comprising anLNT.

Embodiment 584

A catalytic converter comprising: a coated substrate comprising awashcoat layer comprising a PNA material.

Embodiment 585

The catalytic converter of embodiment 584, wherein the PNA materialcomprises an alkali oxide or alkaline earth oxide on a plurality ofmicron-sized support particles.

Embodiment 586

The catalytic converter of any one of embodiments 584-585, wherein thePNA material comprises a second alkali oxide or alkaline earth oxide ona second plurality of micron-sized support particles.

Embodiment 587

The catalytic converter of any one of embodiments 584-586, wherein thePNA material comprises a third alkali oxide or alkaline earth oxide on athird plurality of micron-sized support particles.

Embodiment 588

The catalytic converter of any one of embodiments 584-587, wherein thefirst, second, and third alkali oxides or alkaline earth oxides areselected from the group consisting of manganese oxide, magnesium oxide,and calcium oxide.

Embodiment 589

The catalytic converter of any one of embodiments 584-588, wherein thePNA material comprises PGM.

Embodiment 590

The catalytic converter of embodiment 589, wherein PGM are on a fourthplurality of micron-sized support particles.

Embodiment 591

The catalytic converter of any one of embodiments 589-590, wherein PGMare on at least one of the first, second, or third pluralities ofmicron-sized support particles.

Embodiment 592

The catalytic converter of any one of embodiments 589-591, wherein thePGM comprises platinum, palladium, or a mixture thereof.

Embodiment 593

The catalytic converter of any one of embodiments 589-592, wherein thePGM on a plurality of micron-sized support particles comprises a NNm orNNiM particle.

Embodiment 594

The catalytic converter of any one of embodiments 584-593, wherein thealkali oxides or alkaline earth oxides are nano-sized.

Embodiment 595

The catalytic converter of any one of embodiments 584-594, wherein thepluralities of support particles comprise ceria.

Embodiment 596

The catalytic converter of embodiment 595, wherein the PNA materialcomprises about 150 g/L to about 350 g/L ceria.

Embodiment 597

The catalytic converter of any one of embodiments 584-596, wherein thePNA material stores NOx emissions from ambient temperature to about 100°C.

Embodiment 598

The catalytic converter of any one of embodiments 584-597, wherein thePNA material stores NOx emissions from ambient temperature to about 150°C.

Embodiment 599

The catalytic converter of any one of embodiments 584-598, wherein thePNA material stores NOx emissions from ambient temperature to about 200°C.

Embodiment 600

An exhaust treatment system comprising a conduit for exhaust gas and acatalytic converter comprising a coated substrate comprising a washcoatlayer comprising a PNA material.

Embodiment 601

The exhaust treatment system of embodiment 600, wherein the PNA materialcomprises an alkali oxide or alkaline earth oxide on a plurality ofmicron-sized support particles.

Embodiment 602

The exhaust treatment system of any one of embodiments 600-601, whereinthe PNA material comprises a second alkali oxide or alkaline earth oxideon a second plurality of micron-sized support particles.

Embodiment 603

The exhaust treatment system of any one of embodiments 600-602, whereinthe PNA material comprises a third alkali oxide or alkaline earth oxideon a third plurality of micron-sized support particles.

Embodiment 604

The exhaust treatment system of any one of embodiments 600-603, whereinthe first, second, and third alkali oxides or alkaline earth oxides areselected from the group consisting of manganese oxide, magnesium oxide,and calcium oxide.

Embodiment 605

The exhaust treatment system of any one of embodiments 600-604, whereinthe PNA material comprises PGM.

Embodiment 606

The exhaust treatment system of embodiment 605, wherein PGM are on afourth plurality of micron-sized support particles.

Embodiment 607

The exhaust treatment system of any one of embodiments 605-606, whereinPGM are on at least one of the first, second, or third pluralities ofmicron-sized support particles.

Embodiment 608

The exhaust treatment system of any one of embodiments 605-607, whereinthe PGM comprises platinum, palladium, or a mixture thereof.

Embodiment 609

The exhaust treatment system of any one of embodiments 605-608, whereinthe PGM on a plurality of micron-sized support particles comprises a NNmor NNiM particle.

Embodiment 610

The exhaust treatment system of any one of embodiments 600-609, whereinthe alkali oxides or alkaline earth oxides are nano-sized.

Embodiment 611

The exhaust treatment system of any one of embodiments 600-610, whereinthe pluralities of support particles comprise ceria.

Embodiment 612

The exhaust treatment system of embodiment 611, wherein the PNA materialcomprises about 150 g/L to about 350 g/L ceria.

Embodiment 613

The exhaust treatment system of any one of embodiments 600-612, whereinthe PNA material stores NOx emissions from ambient temperature to about100° C.

Embodiment 614

The exhaust treatment system of any one of embodiments 600-613, whereinthe PNA material stores NOx emissions from ambient temperature to about150° C.

Embodiment 615

The exhaust treatment system of any one of embodiments 600-614, whereinthe PNA material stores NOx emissions from ambient temperature to about200° C.

Embodiment 616

The exhaust treatment system of any one of embodiments 600-615, furthercomprising an SCR unit.

Embodiment 617

The exhaust treatment system of any one of embodiments 600-616, furthercomprising an LNT.

Embodiment 618

A coated substrate comprising: a substrate; and a Passive NOx Adsorber(PNA) layer comprising nano-sized platinum group metal (PGM) on aplurality of support particles comprising cerium oxide.

Embodiment 619

The coated substrate of embodiment 618, wherein the PNA layer stores NOxgas up to at least a first temperature and releases the stored NOx gasat or above the first temperature.

Embodiment 620

The coated substrate of embodiment 619, wherein the first temperature is150° C.

Embodiment 621

The coated substrate of any one of embodiments 618-620, wherein theplurality of support particles are micron-sized.

Embodiment 622

The coated substrate of any one of embodiments 618-620, wherein theplurality of support particles are nano-sized.

Embodiment 623

The coated substrate of any one of embodiments 618-622, wherein theplurality of support particles further comprise zirconium oxide,lanthanum oxide, yttrium oxide, or a combination thereof.

Embodiment 624

The coated substrate of embodiment 623, wherein the plurality of supportparticles comprise HSA5, HSA20, or a mixture thereof.

Embodiment 625

The coated substrate of any of embodiments 618-624, wherein thenano-sized PGM on the plurality of support particles is produced by wetchemistry techniques followed by calcination.

Embodiment 626

The coated substrate of any of embodiments 618-624, wherein thenano-sized PGM on the plurality of support particles is produced byincipient wetness followed by calcination.

Embodiment 627

The coated substrate of any of embodiments 618-620 and 622-624, whereinthe nano-sized PGM on the plurality of support particles comprisecomposite nano-particles, wherein the composite nano-particles comprisea support-nanoparticle and a PGM nano-particle.

Embodiment 628

The coated substrate of embodiment 627, wherein the compositenano-particles are bonded to micron-sized carrier particles to form NNmparticles.

Embodiment 629

The coated substrate of embodiment 627, wherein the compositenano-particles are embedded within carrier particles to form NNiMparticles.

Embodiment 630

The coated substrate of any one of embodiments 628-629, wherein thecarrier particles comprise cerium oxide, zirconium oxide, lanthanumoxide, yttrium oxide, or a combination thereof.

Embodiment 631

The coated substrate of embodiment 630, wherein the carrier particlecomprises 86 wt % cerium oxide, 10 wt % zirconium oxide, and 4 wt %lanthanum oxide.

Embodiment 632

The coated substrate of any one of embodiments 627-631, wherein thecomposite nano-particles are plasma created.

Embodiment 633

The coated substrate of any one of embodiments 618-632, wherein the PGMcomprises palladium.

Embodiment 634

The coated substrate of embodiment 633, wherein the PNA layer comprisesabout 2 g/L to about 4 g/L palladium.

Embodiment 635

The coated substrate of embodiment 634, wherein the PNA layer comprisesabout 3 g/L palladium.

Embodiment 636

The coated substrate of any one of embodiments 633-635, wherein thecoated substrate is used in a greater than or equal to 2.5 L enginesystem.

Embodiment 637

The coated substrate of any one of embodiments 618-632, wherein the PGMcomprises ruthenium.

Embodiment 638

The coated substrate of embodiment 637, wherein the PNA layer comprisesabout 3 g/L to about 15 g/L ruthenium.

Embodiment 639

The coated substrate of embodiment 638, wherein the PNA layer comprisesabout 5 g/L to about 6 g/L ruthenium.

Embodiment 640

The coated substrate of any one of embodiments 637-639, wherein thefirst temperature is 300° C.

Embodiment 641

The coated substrate of any one of embodiments 637-640, wherein thecoated substrate is used in a less than or equal to 2.5 L engine system.

Embodiment 642

The coated substrate of any one of embodiments 618-641, wherein the PNAlayer comprises greater than or equal to about 150 g/L of the pluralityof support particles.

Embodiment 643

The coated substrate of any one of embodiments 618-642, wherein the PNAlayer comprises greater than or equal to about 300 g/L of the pluralityof support particles.

Embodiment 644

The coated substrate of any one of embodiments 618-643, wherein the PNAlayer further comprises boehmite particles.

Embodiment 645

The coated substrate of embodiment 644, wherein the nano-sized PGM onthe plurality of support particles comprises 95% to 98% by weight of themixture of the nano-sized PGM on the plurality of support particles andboehmite particles in the PNA layer.

Embodiment 646

The coated substrate of any one of embodiments 644-645, wherein theboehmite particles comprise 2% to 5% by weight of the mixture of thenano-sized PGM on the plurality of support particles and boehmiteparticles in the PNA layer.

Embodiment 647

The coated substrate of any one of embodiments 618-646, wherein thesubstrate comprises cordierite.

Embodiment 648

The coated substrate of any one of embodiments 618-647, wherein thesubstrate comprises a honeycomb structure.

Embodiment 649

The coated substrate of any one of embodiments 618-648, furthercomprising a corner-fill layer deposited directly on the substrate.

Embodiment 650

A catalytic converter comprising a coated substrate of any one ofembodiments 618-649.

Embodiment 651

An exhaust treatment system comprising a conduit for exhaust gas and acatalytic converter according to embodiment 650.

Embodiment 652

A vehicle comprising a catalytic converter according to embodiment 650.

Embodiment 653

The vehicle of embodiment 652, wherein the vehicle complies with theEuropean emission standard Euro 5.

Embodiment 654

The vehicle of embodiment 652, wherein the vehicle complies with theEuropean emission standard Euro 6.

Embodiment 655

A diesel vehicle comprising a catalytic converter according toembodiment 650.

Embodiment 656

The diesel vehicle of embodiment 655, wherein the diesel vehicle is alight-duty diesel vehicle.

Embodiment 657

A method of treating an exhaust gas, comprising contacting the coatedsubstrate of any one of embodiments 618-649 with the exhaust gas.

Embodiment 658

A method of treating an exhaust gas, comprising contacting the coatedsubstrate of any one of embodiments 618-649 with the exhaust gas,wherein the substrate is housed within a catalytic converter configuredto receive the exhaust gas.

Embodiment 659

A washcoat composition comprising a solids content of: 95% to 98% byweight nano-sized PGM on a plurality of support particles comprisingcerium oxide; and 2% to 5% by weight of boehmite particles.

Embodiment 660

The washcoat composition of embodiment 659, wherein the washcoatcomposition stores NOx gas up to at least 150° C. and releases thestored NOx gas at or above 150° C.

Embodiment 661

The washcoat composition of embodiment 659, wherein the plurality ofsupport particles are micron-sized.

Embodiment 662

The washcoat composition of embodiment 659, wherein the plurality ofsupport particles are nano-sized.

Embodiment 663

The washcoat composition of any one of embodiments 659-662, wherein theplurality of support particles further comprise zirconium oxide,lanthanum oxide, yttrium oxide, or a combination thereof.

Embodiment 664

The washcoat composition of embodiment 663, wherein the plurality ofsupport particles comprise HSA5, HSA20, or a mixture thereof.

Embodiment 665

The washcoat composition of any of embodiments 659-664, wherein thenano-sized PGM on the plurality of support particles is produced by wetchemistry techniques followed by calcination.

Embodiment 666

The washcoat composition of any of embodiments 659-664, wherein thenano-sized PGM on the plurality of support particles is produced byincipient wetness followed by calcination.

Embodiment 667

The washcoat composition of any of embodiments 659-660 and 662-664,wherein the nano-sized PGM on the plurality of support particlescomprise composite nano-particles, wherein the composite nano-particlescomprise a support-nanoparticle and a PGM nano-particle.

Embodiment 668

The washcoat composition of embodiment 667, wherein the compositenano-particles are bonded to micron-sized carrier particles to form NNmparticles.

Embodiment 669

The washcoat composition of embodiment 667, wherein the compositenano-particles are embedded within carrier particles to form NNiMparticles.

Embodiment 670

The washcoat composition of any one of embodiments 668-669, wherein thecarrier particles comprise cerium oxide, zirconium oxide, lanthanumoxide, yttrium oxide, or a combination thereof.

Embodiment 671

The washcoat composition of embodiment 670, wherein the carrier particlecomprises 86 wt % cerium oxide, 10 wt % zirconium oxide, and 4 wt %lanthanum oxide.

Embodiment 672

The washcoat composition of any one of embodiments 667-671, wherein thecomposite nano-particles are plasma created.

Embodiment 673

The washcoat composition of any one of embodiments 659-672, wherein thePGM comprises palladium.

Embodiment 674

The washcoat composition of embodiment 673, wherein the washcoatcomposition comprises about 2 g/L to about 4 g/L palladium.

Embodiment 675

The washcoat composition of embodiment 674, wherein the washcoatcomposition comprises about 3 g/L palladium.

Embodiment 676

The washcoat composition of any one of embodiments 673-675, wherein thewashcoat composition is used in a greater than or equal to 2.5 L enginesystem.

Embodiment 677

The washcoat composition of any one of embodiments 659-672, wherein thePGM comprises ruthenium.

Embodiment 678

The washcoat composition of embodiment 677, wherein the washcoatcomposition comprises about 3 g/L to about 15 g/L ruthenium.

Embodiment 679

The washcoat composition of embodiment 678, wherein the washcoatcomposition comprises about 5 g/L to about 6 g/L ruthenium.

Embodiment 680

The washcoat composition of any one of embodiments 677-679, wherein thewashcoat composition stores NOx gas up to at least 300° C. and releasesthe stored NOx gas at or above 300° C.

Embodiment 681

The washcoat composition of any one of embodiments 677-680, wherein thewashcoat composition is used in a less than or equal to 2.5 L enginesystem.

Embodiment 682

The washcoat composition of any one of embodiments 659-681, wherein thewashcoat composition comprises greater than or equal to about 150 g/L ofthe plurality of support particles.

Embodiment 683

The washcoat composition of any one of embodiments 659-682, wherein thewashcoat composition comprises greater than or equal to about 300 g/L ofthe plurality of support particles.

Embodiment 684

The washcoat composition of any one of embodiments 659-683, wherein thesolids are suspended in an aqueous medium at a pH between 3 and 5.

Embodiment 685

A method of treating an exhaust gas, comprising: contacting a coatedsubstrate with an exhaust gas comprising NOx emissions, wherein thecoated substrate comprises: a substrate; and a PNA layer comprisingnano-sized PGM on a plurality of support particles comprising ceriumoxide.

Embodiment 686

The method of embodiment 685, wherein the PNA layer stores the NOxemissions from the exhaust gas up to at least a first temperature andreleases the stored NOx emissions at or above the first temperature.

Embodiment 687

The method of embodiment 686, wherein the first temperature is 150° C.

Embodiment 688

The method of any one of embodiments 685-687, wherein the plurality ofsupport particles are micron-sized.

Embodiment 689

The method of any one of embodiments 685-687, wherein the plurality ofsupport particles are nano-sized.

Embodiment 690

The method of any one of embodiments 685-689, wherein the plurality ofsupport particles further comprise zirconium oxide, lanthanum oxide,yttrium oxide, or a combination thereof.

Embodiment 691

The method of embodiment 690, wherein the plurality of support particlescomprise HSA5, HSA20, or a mixture thereof.

Embodiment 692

The method of any of embodiments 685-691, wherein the nano-sized PGM onthe plurality of support particles is produced by wet chemistrytechniques followed by calcination.

Embodiment 693

The method of any of embodiments 685-691, wherein the nano-sized PGM onthe plurality of support particles is produced by incipient wetnessfollowed by calcination.

Embodiment 694

The method of any of embodiments 685-687 and 689-691, wherein thenano-sized PGM on the plurality of support particles comprise compositenano-particles, wherein the composite nano-particles comprise asupport-nanoparticle and a PGM nano-particle.

Embodiment 695

The method of embodiment 694, wherein the composite nano-particles arebonded to micron-sized carrier particles to form NNm particles.

Embodiment 696

The method of embodiment 694, wherein the composite nano-particles areembedded within carrier particles to form NNiM particles.

Embodiment 697

The method of any one of embodiments 695-696, wherein the carrierparticles comprise cerium oxide, zirconium oxide, lanthanum oxide,yttrium oxide, or a combination thereof.

Embodiment 698

The method of embodiment 697, wherein the carrier particle comprises 86wt % cerium oxide, 10 wt % zirconium oxide, and 4 wt % lanthanum oxide.

Embodiment 699

The method of any one of embodiments 694-698, wherein the compositenano-particles are plasma created.

Embodiment 700

The method of any one of embodiments 685-699, wherein the PGM comprisespalladium.

Embodiment 701

The method of embodiment 700, wherein the PNA layer comprises about 2g/L to about 4 g/L palladium.

Embodiment 702

The method of embodiment 701, wherein the PNA layer comprises about 3g/L palladium.

Embodiment 703

The method of any one of embodiments 700-702, wherein the exhaust gas isfrom a greater than or equal to 2.5 L engine.

Embodiment 704

The method of any one of embodiments 685-699, wherein the PGM comprisesruthenium.

Embodiment 705

The method of embodiment 704, wherein the PNA layer comprises about 3g/L to about 15 g/L ruthenium.

Embodiment 706

The method of embodiment 705, wherein the PNA layer comprises about 5g/L to about 6 g/L ruthenium.

Embodiment 707

The method of any one of embodiments 704-706, wherein the firsttemperature is 300° C.

Embodiment 708

The method of any one of embodiments 704-707, wherein the exhaust gas isfrom a less than or equal to 2.5 L engine.

Embodiment 709

The method of any one of embodiments 685-708, wherein the PNA layercomprises greater than or equal to about 150 g/L of the plurality ofsupport particles.

Embodiment 710

The method of any one of embodiments 685-709, wherein the PNA layercomprises greater than or equal to about 300 g/L of the plurality ofsupport particles.

Embodiment 711

The method of any one of embodiments 685-710, wherein the PNA layerfurther comprises boehmite particles.

Embodiment 712

The method of embodiment 711, wherein the nano-sized PGM on theplurality of support particles comprises 95% to 98% by weight of themixture of the nano-sized PGM on the plurality of support particles andboehmite particles in the PNA layer.

Embodiment 713

The method of any one of embodiments 711-712, wherein the boehmiteparticles comprise 2% to 5% by weight of the mixture of the nano-sizedPGM on the plurality of support particles and boehmite particles in thePNA layer.

Embodiment 714

The method of any one of embodiments 685-713, wherein the substratecomprises cordierite.

Embodiment 715

The method of any one of embodiments 685-714, wherein the substratecomprises a honeycomb structure.

Embodiment 716

The method of any one of embodiments 685-715, further comprising acorner-fill layer deposited directly on the substrate.

Embodiment 717

A method of forming a coated substrate comprising: coating the substratewith a washcoat composition comprising nano-sized palladium or rutheniumon a plurality of support particles comprising cerium oxide.

Embodiment 718

The method of embodiment 717, wherein the washcoat composition storesNOx gas up to at least 150° C. and releases the stored NOx emissions ator above 150° C.

Embodiment 719

The method of embodiment 717, wherein the plurality of support particlesare micron-sized.

Embodiment 720

The method of embodiment 717, wherein the plurality of support particlesare nano-sized.

Embodiment 721

The method of any one of embodiments 717-720, wherein the plurality ofsupport particles further comprise zirconium oxide, lanthanum oxide,yttrium oxide, or a combination thereof.

Embodiment 722

The method of embodiment 721, wherein the plurality of support particlescomprise HSA5, HSA20, or a mixture thereof.

Embodiment 723

The method of any of embodiments 717-722, wherein the nano-sized PGM onthe plurality of support particles is produced by wet chemistrytechniques followed by calcination.

Embodiment 724

The method of any of embodiments 717-722, wherein the nano-sized PGM onthe plurality of support particles is produced by incipient wetnessfollowed by calcination.

Embodiment 725

The method of any of embodiments 717-718 and 720-722, wherein thenano-sized PGM on the plurality of support particles comprise compositenano-particles, wherein the composite nano-particles comprise asupport-nanoparticle and a PGM nano-particle.

Embodiment 726

The method of embodiment 725, wherein the composite nano-particles arebonded to micron-sized carrier particles to form NNm particles.

Embodiment 727

The method of embodiment 725, wherein the composite nano-particles areembedded within carrier particles to form NNiM particles.

Embodiment 728

The method of any one of embodiments 726-727, wherein the carrierparticles comprise cerium oxide, zirconium oxide, lanthanum oxide,yttrium oxide, or a combination thereof.

Embodiment 729

The method of embodiment 728, wherein the carrier particle comprises 86wt % cerium oxide, 10 wt % zirconium oxide, and 4 wt % lanthanum oxide.

Embodiment 730

The method of any one of embodiments 725-729, wherein the compositenano-particles are plasma created.

Embodiment 731

The method of any one of embodiments 717-730, wherein the washcoatcomposition comprises palladium.

Embodiment 732

The method of embodiment 731, wherein the washcoat composition comprisesabout 2 g/L to about 4 g/L palladium.

Embodiment 733

The method of embodiment 732, wherein the washcoat composition comprisesabout 3 g/L palladium.

Embodiment 734

The method of any one of embodiments 731-733, wherein the coatedsubstrate is used in a greater than or equal to 2.5 L engine system.

Embodiment 735

The method of any one of embodiments 717-730, wherein the washcoatcomposition comprises ruthenium.

Embodiment 736

The method of embodiment 735, wherein the washcoat composition comprisesabout 3 g/L to about 15 g/L ruthenium.

Embodiment 737

The method of embodiment 736, wherein the washcoat composition comprisesabout 5 g/L to about 6 g/L ruthenium.

Embodiment 738

The method of any one of embodiments 735-737, wherein the washcoatcomposition stores NOx gas up to at least 300° C. and releases thestored NOx gas at or above 300° C.

Embodiment 739

The method of any one of embodiments 735-738, wherein the coatedsubstrate is used in a less than or equal to 2.5 L engine system.

Embodiment 740

The method of any one of embodiments 717-739, wherein the washcoatcomposition comprises greater than or equal to about 150 g/L of theplurality of support particles.

Embodiment 741

The method of any one of embodiments 717-740, wherein the washcoatcomposition comprises greater than or equal to about 300 g/L of theplurality of support particles.

Embodiment 742

The method of any one of embodiments 717-741, wherein the washcoatcomposition further comprises boehmite particles.

Embodiment 743

The method of embodiment 742, wherein the nano-sized PGM on a pluralityof support particles comprises 95% to 98% by weight of the mixture ofnano-sized PGM on a plurality of support particles and boehmiteparticles in the washcoat composition.

Embodiment 744

The method of any one of embodiments 742-743, wherein the boehmiteparticles comprise 2% to 5% by weight of the mixture of nano-sized PGMon a plurality of support particles and boehmite particles in thewashcoat composition.

Embodiment 745

The method of any one of embodiments 717-744, wherein the substratecomprises cordierite.

Embodiment 746

The method of any one of embodiments 717-745, wherein the substratecomprises a honeycomb structure.

Embodiment 747

The method of any one of embodiments 717-746, further comprising coatingthe substrate with a corner-fill washcoat prior to coating the substratewith the PNA washcoat.

Embodiment 748

A method of forming a coated substrate, the method comprising: coatingthe substrate with a washcoat composition according to any one ofembodiments 659-684.

Embodiment 749

The method of embodiment 748, further comprising coating the substratewith a corner-fill washcoat prior to coating the substrate with the PNAwashcoat.

Embodiment 750

A catalytic converter comprising a coated substrate according to any oneof embodiments 748-749.

Embodiment 751

An exhaust treatment system comprising a conduit for exhaust gas and acatalytic converter according to embodiment 750.

Embodiment 752

A vehicle comprising a catalytic converter according to embodiment 750.

Embodiment 753

The vehicle of embodiment 752, wherein the vehicle complies with theEuropean emission standard Euro 5.

Embodiment 754

The vehicle of embodiment 752, wherein the vehicle complies with theEuropean emission standard Euro 6.

Embodiment 755

A diesel vehicle comprising a catalytic converter according toembodiment 750.

Embodiment 756

The diesel vehicle of embodiment 755, wherein the diesel vehicle is alight-duty diesel vehicle.

Embodiment 757

A coated substrate comprising a washcoat composition according to anyone of embodiments 659-684.

Embodiment 758

A vehicle comprising: a catalytic converter comprising a PNA layercomprising nano-sized PGM on a plurality of support particles comprisingcerium oxide, wherein the vehicle complies with the European emissionstandard Euro 5.

Embodiment 759

The vehicle of embodiment 758, wherein the PNA layer stores NOxemissions from an engine of the vehicle up to at least a firsttemperature and releases the stored NOx emissions at or above the firsttemperature.

Embodiment 760

The vehicle of embodiment 759, wherein the first temperature is 150° C.

Embodiment 761

The vehicle of embodiment 758, wherein the plurality of supportparticles are micron-sized.

Embodiment 762

The vehicle of embodiment 758, wherein the plurality of supportparticles are nano-sized.

Embodiment 763

The vehicle of any one of embodiments 758-762, wherein the plurality ofsupport particles further comprise zirconium oxide, lanthanum oxide,yttrium oxide, or a combination thereof.

Embodiment 764

The vehicle of embodiment 763, wherein the plurality of supportparticles comprise HSA5, HSA20, or a mixture thereof.

Embodiment 765

The vehicle of any of embodiments 758-764, wherein the nano-sized PGM onthe plurality of support particles is produced by wet chemistrytechniques followed by calcination.

Embodiment 766

The vehicle of any of embodiments 758-764, wherein the nano-sized PGM onthe plurality of support particles is produced by incipient wetnessfollowed by calcination.

Embodiment 767

The vehicle of any of embodiments 758-760 and 762-764, wherein thenano-sized PGM on the plurality of support particles comprise compositenano-particles, wherein the composite nano-particles comprise asupport-nanoparticle and a PGM nano-particle.

Embodiment 768

The vehicle of embodiment 767, wherein the composite nano-particles arebonded to micron-sized carrier particles to form NNm particles.

Embodiment 769

The vehicle of embodiment 767, wherein the composite nano-particles areembedded within carrier particles to form NNiM particles.

Embodiment 770

The vehicle of any one of embodiments 768-769, wherein the carrierparticles comprise cerium oxide, zirconium oxide, lanthanum oxide,yttrium oxide, or a combination thereof.

Embodiment 771

The vehicle of embodiment 770, wherein the carrier particle comprises 86wt % cerium oxide, 10 wt % zirconium oxide, and 4 wt % lanthanum oxide.

Embodiment 772

The vehicle of any one of embodiments 767-771, wherein the compositenano-particles are plasma created.

Embodiment 773

The vehicle of any one of embodiments 758-772, wherein the PGM comprisespalladium.

Embodiment 774

The vehicle of embodiment 773, wherein the PNA layer comprises about 2g/L to about 4 g/L palladium.

Embodiment 775

The vehicle of embodiment 774, wherein the PNA layer comprises about 3g/L palladium.

Embodiment 776

The vehicle of any one of embodiments 773-775, wherein the engine isgreater than or equal to 2.5 L.

Embodiment 777

The vehicle of any one of embodiments 758-772, wherein the PGM comprisesruthenium.

Embodiment 778

The vehicle of embodiment 777, wherein the PNA layer comprises about 3g/L to about 15 g/L ruthenium.

Embodiment 779

The vehicle of embodiment 778, wherein the PNA layer comprises about 5g/L to about 6 g/L ruthenium.

Embodiment 780

The vehicle of any one of embodiments 777-779, wherein the firsttemperature is 300° C.

Embodiment 781

The vehicle of any one of embodiments 777-780, wherein the engine isless than or equal to 2.5 L.

Embodiment 782

The vehicle of any one of embodiments 758-781, wherein the PNA layercomprises greater than or equal to about 150 g/L of the plurality ofsupport particles.

Embodiment 783

The vehicle of any one of embodiments 758-782, wherein the PNA layercomprises greater than or equal to about 300 g/L of the plurality ofsupport particles.

Embodiment 784

The vehicle of any one of embodiments 758-783, wherein the vehicle is adiesel vehicle.

Embodiment 785

The vehicle of embodiment 784, wherein the diesel vehicle is alight-duty diesel vehicle.

Embodiment 786

The vehicle of any one of embodiments 758-785, further comprising an SCRunit downstream the catalytic converter.

Embodiment 787

The vehicle of any one of embodiments 758-786, further comprising anLNT.

Embodiment 788

The vehicle of any one of embodiments 758-787, wherein the vehiclecomplies with European emission standard Euro 6.

Embodiment 789

A catalytic converter comprising: a coated substrate comprising a PNAlayer comprising nano-sized PGM on a plurality of support particlescomprising cerium oxide.

Embodiment 790

The catalytic converter of embodiment 789, wherein the PNA layer storesNOx gas up to at least 150° C. and releases the stored NOx gas at orabove 150° C.

Embodiment 791

The catalytic converter of embodiment 789, wherein the plurality ofsupport particles are micron-sized.

Embodiment 792

The catalytic converter of embodiment 789, wherein the plurality ofsupport particles are nano-sized.

Embodiment 793

The catalytic converter of any one of embodiments 789-792, wherein theplurality of support particles further comprise zirconium oxide,lanthanum oxide, yttrium oxide, or a combination thereof.

Embodiment 794

The catalytic converter of embodiment 793, wherein the plurality ofsupport particles comprise HSA5, HSA20, or a mixture thereof.

Embodiment 795

The catalytic converter of any of embodiments 789-794, wherein thenano-sized PGM on the plurality of support particles is produced by wetchemistry techniques followed by calcination.

Embodiment 796

The catalytic converter of any of embodiments 789-794, wherein thenano-sized PGM on the plurality of support particles is produced byincipient wetness followed by calcination.

Embodiment 797

The catalytic converter of any of embodiments 789-173 and 792-794,wherein the nano-sized PGM on the plurality of support particlescomprise composite nano-particles, wherein the composite nano-particlescomprise a support-nanoparticle and a PGM nano-particle.

Embodiment 798

The catalytic converter of embodiment 797, wherein the compositenano-particles are bonded to micron-sized carrier particles to form NNmparticles.

Embodiment 799

The catalytic converter of embodiment 797, wherein the compositenano-particles are embedded within carrier particles to form NNiMparticles.

Embodiment 800

The catalytic converter of any one of embodiments 798-799, wherein thecarrier particles comprise cerium oxide, zirconium oxide, lanthanumoxide, yttrium oxide, or a combination thereof.

Embodiment 801

The catalytic converter of embodiment 800, wherein the carrier particlecomprises 86 wt % cerium oxide, 10 wt % zirconium oxide, and 4 wt %lanthanum oxide.

Embodiment 802

The catalytic converter of any one of embodiments 797-801, wherein thecomposite nano-particles are plasma created.

Embodiment 803

The catalytic converter of any one of embodiments 789-802, wherein thePGM comprises palladium.

Embodiment 804

The catalytic converter of embodiment 803, wherein the PNA layercomprises about 2 g/L to about 4 g/L palladium.

Embodiment 805

The catalytic converter of embodiment 804, wherein the PNA layercomprises about 3 g/L palladium.

Embodiment 806

The catalytic converter of any one of embodiments 803-805, wherein thecatalytic converter is used in at least a 2.5 L engine system.

Embodiment 807

The catalytic converter of any one of embodiments 789-802, wherein thePGM comprises ruthenium.

Embodiment 808

The catalytic converter of embodiment 807, wherein the PNA layercomprises about 3 g/L to about 15 g/L ruthenium.

Embodiment 809

The catalytic converter of embodiment 808, wherein the PNA layercomprises about 5 g/L to about 6 g/L ruthenium.

Embodiment 810

The catalytic converter of any one of embodiments 807-809, wherein thePNA layer stores NOx gas up to at least 300° C. and releases the storedNOx gas at or above 300° C.

Embodiment 811

The catalytic converter of any one of embodiments 807-810, wherein thecatalytic converter is used in at most a 2.5 L engine system.

Embodiment 812

The catalytic converter of any one of embodiments 789-811, wherein thePNA layer comprises greater than or equal to about 150 g/L of theplurality of support particles.

Embodiment 813

The catalytic converter of any one of embodiments 789-812, wherein thePNA layer comprises greater than or equal to about 300 g/L of theplurality of support particles.

Embodiment 814

An exhaust treatment system comprising a conduit for exhaust gascomprising NOx emissions and a catalytic converter comprising a coatedsubstrate comprising a PNA layer comprising nano-sized PGM on aplurality of support particles comprising cerium oxide.

Embodiment 815

The exhaust treatment system of embodiment 814, wherein the PNA layerstores the NOx emissions from the exhaust gas up to at least 150° C. andreleases the stored NOx emissions at or above 150° C.

Embodiment 816

The exhaust treatment system of embodiment 814, wherein the plurality ofsupport particles are micron-sized.

Embodiment 817

The exhaust treatment system of embodiment 814, wherein the plurality ofsupport particles are nano-sized.

Embodiment 818

The exhaust treatment system of any one of embodiments 814-817, whereinthe plurality of support particles further comprise zirconium oxide,lanthanum oxide, yttrium oxide, or a combination thereof.

Embodiment 819

The exhaust treatment system of embodiment 818, wherein the plurality ofsupport particles comprise HSA5, HSA20, or a mixture thereof.

Embodiment 820

The exhaust treatment system of any of embodiments 814-819, wherein thenano-sized PGM on the plurality of support particles is produced by wetchemistry techniques followed by calcination.

Embodiment 821

The exhaust treatment system of any of embodiments 814-819, wherein thenano-sized PGM on the plurality of support particles is produced byincipient wetness followed by calcination.

Embodiment 822

The exhaust treatment system of any of embodiments 814-815 and 817-819,wherein the nano-sized PGM on the plurality of support particlescomprise composite nano-particles, wherein the composite nano-particlescomprise a support-nanoparticle and a PGM nano-particle.

Embodiment 823

The exhaust treatment system of embodiment 822, wherein the compositenano-particles are bonded to micron-sized carrier particles to form NNmparticles.

Embodiment 824

The exhaust treatment system of embodiment 823, wherein the compositenano-particles are embedded within carrier particles to form NNiMparticles.

Embodiment 825

The exhaust treatment system of any one of embodiments 823-824, whereinthe carrier particles comprise cerium oxide, zirconium oxide, lanthanumoxide, yttrium oxide, or a combination thereof.

Embodiment 826

The exhaust treatment system of embodiment 825, wherein the carrierparticle comprises 86 wt % cerium oxide, 10 wt % zirconium oxide, and 4wt % lanthanum oxide.

Embodiment 827

The exhaust treatment system of any one of embodiments 822-826, whereinthe composite nano-particles are plasma created.

Embodiment 828

The exhaust treatment system of any one of embodiments 814-827, whereinthe PGM comprises palladium.

Embodiment 829

The exhaust treatment system of embodiment 828, wherein the PNA layercomprises about 2 g/L to about 4 g/L palladium.

Embodiment 830

The exhaust treatment system of embodiment 829, wherein the PNA layercomprises about 3 g/L palladium.

Embodiment 831

The exhaust treatment system of any one of embodiments 828-830, whereinthe exhaust gas is from at least a 2.5 L engine.

Embodiment 832

The exhaust treatment system of any one of embodiments 814-827, whereinthe PGM comprises ruthenium.

Embodiment 833

The exhaust treatment system of embodiment 832, wherein the PNA layercomprises about 3 g/L to about 15 g/L ruthenium.

Embodiment 834

The exhaust treatment system of embodiment 833, wherein the PNA layercomprises about 5 g/L to about 6 g/L ruthenium.

Embodiment 835

The exhaust treatment system of any one of embodiments 832-834, whereinthe PNA layer stores NOx emissions from the exhaust gas up to at least300° C. and releases the stored NOx emissions at or above 300° C.

Embodiment 836

The exhaust treatment system of any one of embodiments 832-835, whereinthe exhaust gas is from at most a 2.5 L engine.

Embodiment 837

The exhaust treatment system of any one of embodiments 814-836, whereinthe PNA layer comprises greater than or equal to about 150 g/L of theplurality of support particles.

Embodiment 838

The exhaust treatment system of any one of embodiments 814-837, whereinthe PNA layer comprises greater than or equal to about 300 g/L of theplurality of support particles.

Embodiment 839

The exhaust treatment system of any one of embodiments 814-838, furthercomprising an SCR unit downstream the catalytic converter.

Embodiment 840

The exhaust treatment system of any one of embodiments 814-839, furthercomprising an LNT.

Embodiment 841

The exhaust treatment system of any one of embodiments 814-840, whereinthe exhaust treatment system complies with European emission standardEuro 5.

Embodiment 842

The exhaust treatment system of any one of embodiments 814-841, whereinthe exhaust treatment system complies with European emission standardEuro 6.

EXAMPLES

As discussed above, the washcoat compositions can be configured andapplied in a variety of different ways. The configurations provideexamples of preparing substrates coated with the washcoats.

General Procedure for Preparation of Washcoats

The washcoats are made by mixing the solid ingredients with water.Acetic acid is added to adjust the pH to about 4. The washcoat slurry isthen milled to arrive at an average particle size of about 4 μm to about15 μm. The viscosity of the washcoat is adjusted by mixing with acellulose solution or with corn starch to the desired viscosity,typically between about 300 cP to about 1200 cP. The washcoat is agedfor about 24 hours to about 48 hours after cellulose or corn starchaddition. The washcoat is coated onto the substrate by eitherdip-coating or vacuum coating. The part(s) to be coated can beoptionally pre-wetted prior to coating. Excess washcoat is blown off andrecycled. The washcoat-coated substrate is then dried at about 25° C. toabout 95° C. by flowing air over the coated part, until the weightlevels off. The washcoat-coated substrate is then calcined at about 450°C. to about 650° C. for about 1 hour to about 2 hours.

Testing the PNA Material for NO_(x) Storage and Release

The performance of various PNA materials were tested for NO_(x) storageand release temperatures. In order to test the performance of thevarious PNA materials, the following process was adhered to: (1) buildthe actual PNA samples; (2) age the samples hydrothermally; (3) test thesamples for NO_(x) emission storage and release using a synthetic gasmixture that mimics the exhaust of a light duty diesel vehicle. Theresults shown in FIGS. 5-7 are “second runs” (i.e., the PNA samples wererun back to back to see whether there was any residual storage effects).Based on the results shown in FIGS. 5-7, there were none and the PNAmaterials release 100% of the stored NO_(x) emissions.

The following Tables 1 and 2 list the Aging Conditions and TestingProtocol used to test the PNA samples.

TABLE 1 Aging Conditions Heating Rate 2 hrs (=6.7° C./min) Temperature750° C. Holding Period 20 hrs Cool Down Rate <3° C./min Atmosphere H₂O(~5%), O₂ (20%), N₂ (rest) Volumetric Flow N/A

TABLE 2 Testing Protocol Sample Size 1″ × 1″core GHSV 60,000 h⁻¹ GasMixture Propene = 400 ppm CO = 1,200 ppm NO = 50 ppm O₂ = 12.5% CO₂ = 6%H₂O = 6.5% N₂ = Rest Heating Rate 5° C./min (100° C.-350° C.)

FIG. 5 is a graph showing the NO_(x) emission adsorption and release formanganese based PNA material across an operating temperature spectrum.As shown in FIG. 5, manganese based PNA material stores NO_(x) emissionsefficiently up to about 110° C. At that point, the PNA material stopsadsorbing NO_(x) emissions and starts releasing the adsorbed NO_(x). Atabout 220° C., all the stored NO_(x) emissions are released. Thus,manganese based oxides are good NO_(x) emission adsorbers from ambienttemperature to about 100° C. In addition, the manganese based oxidesexhibited a “sharp” release temperature. The slight drop in NO slippageat 110° C. is due to water being turned on.

FIG. 6 is a graph showing the NO_(x) emission adsorption and release formagnesium based PNA material across an operating temperature spectrum.As shown in FIG. 6, magnesium based PNA material stores NO_(x) emissionsefficiently up to about 150° C. At that point, the PNA material stopsadsorbing NO_(x) emissions and starts releasing the adsorbed NO_(x). Atabout 240° C., all the stored NO_(x) emissions are released. Thus,magnesium based oxides are good NO_(x) emission adsorbers from ambienttemperature to about 150° C. In addition, the magnesium based oxidesexhibited a “sharp” release temperature. The sharp drop in NO slippageat 110° C. is due to water being turned on.

FIG. 7 is a graph showing the NO_(x) emission adsorption and release forcalcium based PNA material across an operating temperature spectrum. Asshown in FIG. 7, calcium based PNA material stores NO_(x) emissionsefficiently up to about 180° C. At that point, the PNA material stopsadsorbing NO_(x) emissions and starts releasing the adsorbed NO_(x). Atabout 310° C., all the stored NO_(x) emissions are released. Thus,calcium based oxides are good NO_(x) emission adsorbers from ambienttemperature to about 150° C. In addition, the calcium based oxidesexhibited a “sharp” release temperature. The sharp drop in NO slippageat 110° C. is due to water being turned on.

FIG. 8 illustrates NO_(x) emission storage comparison performance of oneembodiment of a catalytic converter employing a substrate coated withpalladium based PNA material and a platinum group metal loading of theentire catalytic converter of about 2.5 g/l (catalytic converter A,dashed line) to the performance of a commercially available catalyticconverter (catalytic converter B, solid line) with a platinum groupmetal loading of the entire catalytic converter of about 6.4 g/l.

Catalytic converter A (employing PNA material as described herein) wasformed by generating a PNA washcoat including palladium on cerium oxideproduced by wet chemistry methods and boehmite. The PNA washcoat wascoated onto a first zone of the substrate and the substrate was driedand calcined. On a second zone of the substrate downstream the PNA zone,the substrate had a corner fill layer, a catalytic layer (on top of thecorner fill layer) including NNm particles and a Pt:Pd weight ratio of2:1, and a zeolite layer (on top of the catalytic layer), all of whichas described herein. Catalytic converter B is a commercially availablecatalytic converter formed by wet chemistry methods. Both catalyticconverters were tested under the same conditions.

As shown in FIG. 8, as the temperature of the catalytic converter Bincreased, the NO_(x) emissions increased linearly. In contrast, as thetemperature of the catalytic converter A increased, the NO_(x) emissionsonly slightly increased until after a designated time and temperature,wherein the NO_(x) emissions were sharply released. Accordingly,catalytic converter A was able to store NO_(x) emissions from ambient upto about 150° C.

FIG. 9 illustrates a comparison of the tailpipe emissions of thecatalytic converter A and the catalytic converter B. As shown in FIG. 9,catalytic converter A can have about 50% less CO emissions thancatalytic converter B and use significantly less PGM thereby reducingcost.

The disclosures of all publications, patents, patent applications, andpublished patent applications referred to herein by an identifyingcitation are hereby incorporated herein by reference in their entirety.

The present invention has been described in terms of specificembodiments incorporating details to facilitate the understanding ofprinciples of construction and operation of the invention. Suchreference herein to specific embodiments and details thereof is notintended to limit the scope of the claims appended hereto. It will bereadily apparent to one skilled in the art that other variousmodifications can be made in the embodiments chosen for illustrationwithout departing from the spirit and scope of the invention. Therefore,the description and examples should not be construed as limiting thescope of the invention.

We claim:
 1. A method of treating an exhaust gas, comprising: contactinga coated substrate with an exhaust gas comprising NO_(x) emissions,wherein the coated substrate comprises: a substrate; and a Passive NOxAdsorber (PNA) layer comprising nano-sized platinum group metal (PGM) ona plurality of support particles comprising cerium oxide, wherein theamount of cerium oxide used in the PNA layer is from about 50 g/L toabout 400 g/L.
 2. The method of claim 1, wherein the PNA layer storesNOx gas up to at least a first temperature and releases the stored NOxgas at or above the first temperature.
 3. The method of claim 2, whereinthe first temperature is 150° C.
 4. The method of claim 2, wherein thePGM comprises ruthenium, the PNA layer stores NOx gas up to at least a300° C. and releases the stored NOx gas at or above 300° C.
 5. Themethod of claim 1, wherein the plurality of support particles aremicron-sized or the plurality of support particles are nano-sized. 6.The method of claim 1, wherein the plurality of support particlesfurther comprise zirconium oxide, lanthanum oxide, yttrium oxide, or acombination thereof.
 7. The method of claim 1, wherein the nano-sizedPGM on the plurality of support particles comprise compositenano-particles, wherein the composite nano-particles comprise asupport-nano-particle and a PGM nano-particle.
 8. The method of claim 7,wherein the composite nano-particles are bonded to micron-sized carrierparticles to form nano-on-nano-on-micro particles.
 9. The method ofclaim 8, wherein the micron-sized carrier particles comprise ceriumoxide, zirconium oxide, lanthanum oxide, yttrium oxide, or a combinationthereof.
 10. The method of claim 8, wherein the micron-sized carrierparticles comprise 86 wt % cerium oxide, 10 wt % zirconium oxide, and 4wt % lanthanum oxide.
 11. The method of claim 7, wherein the compositenano-particles are embedded within carrier particles to formnano-on-nano-in-micro particles.
 12. The method of claim 7, wherein thecomposite nanoparticles are plasma created.
 13. The method of claim 1,wherein the PGM comprises palladium and/or ruthenium.
 14. The method ofclaim 1, wherein the PNA layer comprises about 2 g/L to about 4 g/Lpalladium and/or about 3 g/L to about 15 g/L ruthenium.
 15. The methodof claim 1, wherein the PNA layer comprises greater than or equal toabout 150 g/L of the plurality of support particles.
 16. The method ofclaim 1, wherein the PNA layer further comprises boehmite particles. 17.The method of claim 16, wherein the nano-sized PGM on the plurality ofsupport particles comprises 95% to 98% by weight of the mixture of thenano-sized PGM on the plurality of support particles and the boehmiteparticles in the PNA layer and/or the boehmite particles comprise 2% to5% by weight of the mixture of the nano-sized PGM on the plurality ofsupport particles and boehmite particles in the PNA layer.
 18. Themethod of claim 1, wherein the substrate comprises cordierite.
 19. Themethod of claim 1, wherein the substrate comprises a honeycombstructure.
 20. The method of claim 1, wherein a corner-fill layer isdeposited directly on the substrate.